Pyrazole sulfonates

ABSTRACT

Herbicidal compositions containing as an active ingredient one or more of the pyrazole compounds having the formula ##STR1## (wherein R 1  represents hydrogen atom or a lower alkyl group, R 2  represents a lower alkyl group or a lower alkenyl group, X represents a halogen atom, nitro group, a lower alkyl group, a halogenated lower alkyl group, a lower alkoxy group, a lower alkanesulfonyl group, cyano group, a lower alkylthio group or an aliphatic acyl group and n is an integer of 1 to 4 and when n is 2, 3 or 4, X&#39;s may be the same or different), salts thereof and organic acid esters thereof, as well as new pyrazole compounds having herbicidal activities and the formula ##STR2## (wherein R 1  represents hydrogen atom or a lower alkyl group, R 2  represents a lower alkyl group or a lower alkenyl group Z represents a halogen atom, nitro group, a lower alkyl group, a halogenated lower alkyl group, a lower alkoxy group, a lower alkanesulfonyl group, cyano group, a lower alkylthio group, an aliphatic acyl group or benzoyl group, n is an integer of 1 to 4, when n is 2, 3 or 4, Z&#39;s may be the same or different and Y represents oxygen atom or sulfur atom); provided that those wherein R 1  and R 2  are methyl groups, Z is chlorine atom at 2-position, n is 1 and Y is oxygen atom and wherein R 1  and R 2  are methyl groups, Z is nitro group at 4-position, n is 1 and Y is oxygen atom are excluded. These pyrazole compounds are prepared in a conventional manner.

This is a division of application Ser. No. 558,682, filed on Mar. 17,1975, now U.S. Pat. No. 4,063,925.

This invention relates to the use of pyrazole derivatives as a herbicideand also to a certain group of new pyrazole derivatives.

More particularly, it is concerned with a herbicidal composition whichcomprises as an active ingredient a compound having the formula ##STR3##(wherein R₁ represents a hydrogen atom or a lower alkyl group, R₂represents a lower alkyl group or a lower alkenyl group, X represents ahalogen atom, nitro group, a lower alkyl group, a halogenated loweralkyl group, a lower alkoxy group, a lower alkanesulfonyl group, cyanogroup, a lower alkylthio group or an aliphatic acyl group and n is aninteger of 1 to 4 and when n is 2, 3 or 4, X's may be the same ordifferent), a salt thereof or an organic acid ester thereof, and anagriculturally acceptable carrier, with a method for the destruction ofundesirable weeds which comprises applying to said weeds a herbicidalamount of the compound having the above formula (I), as well as withsome new pyrazole derivatives having the formula ##STR4## (wherein R₁represents hydrogen atom or a lower alkyl group, R₂ represents a loweralkyl group or a lower alkenyl group, Z represents a halogen atom, nitrogroup, a lower alkyl group, a halogenated lower alkyl group, a loweralkoxy group, a lower alkanesulfonyl group, cyano group, a loweralkylthio group, an aliphatic acyl group or benzoyl group, n is aninteger of 1 to 4, when n is 2, 3 or 4, Z's may be the same or differentand Y represents oxygen atom or sulfur atom); provided that thosewherein R₁ and R₂ are methyl groups, Z is chlorine atom at 2-position, nis 1 and Y is oxygen atom and wherein R₁ and R₂ are methyl groups, Z isnitro group at 4-position, n is 1 and Y is oxygen atom are excluded.

The compounds of the above-mentioned formula (I) may be present in theform of the tautomerism as shown under. ##STR5## (wherein R₁, R₂, X, andn have the same meanings as above). It is, of course, to be noted thatthe same tantomerism as shown above may be observed with respect to thecompounds (II).

In the above-mentioned formula (I), R₁ is preferably hydrogen atom; astraight or branched lower alkyl group having 1 to 6 carbon atoms,particularly 1 to 3 carbon atoms, methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-amyl,2-methylbutyl, tert-amyl, n-hexyl, 2-hexyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 3-hexyl, 2-ethylbutyl, 2-methyl-2-pentylor 2,2-dimethylbutyl. R₂ preferably is a straight or branched loweralkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbonatoms, as exemplified with regard to R₁ and a straight or branched loweralkenyl group having 3 to 6 carbon atoms, particularly 3 or 4 carbonatoms such as allyl, 2-butenyl, 1-methyl-2-propenyl,2-methyl-2-propenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-butenyl,1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-2-butenyl, 3-pentenyl,2 -hexenyl, 3-hexenyl or 4-hexenyl. X is preferably a halogen atom suchas chlorine, bromine, fluorine or iodine; nitro group; a straight orbranched lower alkyl group having 1 to 4 carbon atoms such as methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert.-butyl,particularly methyl group; a lower alkyl group having 1 to 2 carbonatoms and substituted with 1 to 3 halogen atoms such as trifluoromethyl,2,2,2-trichloroethyl, 2,2-dibromoethyl, 2,2,2-tribromoethyl, 2-iodoethylor 2,2-diiodoethyl; a straight or branched lower alkoxy group having 1to 4 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy or isobutoxy, particularly methoxy group; a straight orbranched lower alkanesulfonyl group having 1 to 4 carbon atoms such asmethanesulfonyl, ethanesulfonyl, 1-propanesulfonyl, 2-propanesulfonyl,1-butanesulfonyl or 2-butanesulfonyl, particularly methanesulfonylgroup; cyano group; a straight or branched lower alkylthio group having1 to 4 carbon atoms such as methylthio, ethylthio, n-propylthio,isopropylthio, n-butylthio or isobutylthio; an aliphatic acyl group suchas a straight or branched lower alkanoyl group having 2 to 5 carbonatoms such as acetyl, propionyl, butyryl or pivaloyl.

The salts of the compounds of the above-mentioned formula (I) includethe salts with monovalent to trivalent metallic ions such as sodium,potassium, calcium, magnesium, aluminum, iron, manganese, zinc, nickel,cobalt or copper; the salts with complex ions such as [Cu(H₂ O)₂ ]⁺⁺,[Mn(H₂ O)₂ ]⁺⁺, [Ni(H₂ O)₄ ]⁺⁺, [A (OH)]⁺⁺, [Zn(OH)]⁺, [Cu(OH)]⁺,[Cu(NH₃)₂ ]⁺⁺ or [Co(NH₂ CH₂ CH₂ NH₂)]⁺⁺ ; the salts with ammonium ionsuch as N⁺ H₄, N⁺ H(CH₃)₃, N⁺ H₂ (C₂ H₅)₂, N⁺ H₃ CH(CH₃)₂, N⁺ H₃ CH₂ CH₂OH or N⁺ H₃ CH₂ CH₂ OC₂ H₅ ; the salts with mineral acids such ashydrochloric acid, sulfuric acid, nitric acid or hydrobromic acid.

The organic acid esters of the compound of the above-mentioned formula(I) may be esters of those organic acids that are capable of forming thecorresponding esters at the 5-position in the pyrazole ring and alsoconverting to the original compounds (I) by decomposition uponapplication. These organic acids are contemplated to include

(1) an aliphatic, alicyclic or aromatic carboxylic acid of the formula

    R.sub.3 COOH

wherein R₃ is a straight or branched alkyl group having 1 to 17 carbonatoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,tert.-butyl, heptyl, undecyl, tetradecyl or heptadecyl; a lower alkylgroup having 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms, andsubstituted with 1 to 4 halogen atoms such as chloromethyl, bromomethyl,iodomethyl, 2,2,2-trichloroethyl, 2,2-dibromoethyl, 2,2,2-tribromoethyl,2-iodoethyl, 2,2-diiodoethyl, or 1,1,2,2-tetrafluoroethyl; a straight orbranched alkenyl group having 2-17 carbon atoms, particularly 3-5 carbonatoms, such as vinyl, isopropenyl, allyl, 1-methyl-2-propenyl,2-methyl-2-propenyl, 2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,3-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 2-heptenyl,2-undecenyl, 2-tetradecenyl, 2-heptadecenyl, 3-heptadecenyl or8,11-heptadecadienyl; a 5- to 7-membered cycloalkyl group such ascyclopentyl, cyclohexyl or cycloheptyl; a phenyl group which may have 1to 3 substituents of nitro, halogen and/or alkyl of 1 to 4 carbon atoms,particularly 1 carbon atom, such as phenyl, 2-nitrophenyl,4-nitrophenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2-chlorophenyl,4-chlorophenyl, 2-bromophenyl, 4-bromophenyl, 2,4-dichlorophenyl,2,4,6-trichlorophenyl or 2-chloro-4-nitrophenyl; a phenylalkyl groupwhich may have 1-3 of nitro and/or halogen as substituents in the phenylmoiety and has 1-5 carbon atoms, particularly 1 or 2 carbon atoms suchas benzyl, phenethyl, phenylpropyl, phenylbutyl, phenylpentyl,4-nitrobenzyl, 4-nitrophenethyl, 2-chlorobenzyl, 4-chlorophenethyl,2-bromobenzyl, 4-bromophenethyl, 3-(2,4-dichlorophenyl)propyl or4-(2,4,6-trichlorophenyl)butyl; styryl group; or a phenoxyalkyl groupwhich may have 1 or 2 of halogen and/or methyl as substituents in thephenyl moiety and has 1 to 3 carbon atoms,

(2) a carbamic acid of the formula ##STR6## wherein R₄ and R₅individually represent a straight or branched lower alkyl group having1-4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl orisobutyl or R₄ and R₅ jointly represent pentamethylene group,

(3) a sulfonic acid of the formula

    R.sub.6 -- SO.sub.2 -- OH

wherein R₆ represents a straight or branched lower alkyl group having1-4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl orisobutyl; a lower alkyl group substituted with 1-3 halogens and having1-3 carbon atoms, particularly 1 or 2 carbon atoms such as chloromethyl,bromomethyl, iodomethyl, trifluoromethyl, 1-chloroethyl, 1-bromoethyl or1,1-dichloroethyl; or a phenyl group which may have straight or branchedalkyl of 1-12 carbon atoms particularly 1 or 2 carbon atoms, e.g.,methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or dodecyl orhalogen, e.g., chloro as substituents,

(4) a diester of thiophosphoric acid of the formula ##STR7## wherein R₇'s may be the same or different and represent a straight or branchedlower alkyl group having 1-4 carbon atoms such as methyl, ethyl,n-propyl, isopropyl, n-butyl or isobutyl,

(5) a monoester of carbonic or thiocarbonic acid of the formula ##STR8##wherein R₈ represents a straight or branched lower alkyl group having1-4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl or sec.-butyl; phenyl group; oor a phenylalkyl group which mayhave as substituents 1-3 of nitro and/or halogen in the phenyl moietyand has 1 or 2 carbon atoms in the alkyl moiety such as benzyl,phenethyl, 4-nitrobenzyl, 2-chlorobenzyl, 4-chlorophenethyl,2-bromobenzyl, 2,4-dichlorobenzyl or 2,4,6-trichlorobenzyl and Yrepresents oxygen atom or sulfur atom,

(6) a dibasic acid of the formula ##STR9## wherein m is 0 or 1, R₉ is analkylene group having 1 to 10 carbon atoms such as methylene, ethylene,trimethylene, tetramethylene, octamethylene or decamethylene; vinylenegroup; or o-, m- or p-phenylene group or both C═O may be linked withoutR₉ and, when m is zero, only the dibasic acid ##STR10## being includedwithin the scope of this formula, and

(7) a 3-oxo-4-isoxazolin-2-yl carboxylic acid of the formula ##STR11##wherein R₁₀ is hydrogen atom or a halogen atom.

In agricultural chemicals field, there were previously proposed varioustypes of compounds as a herbicide and many of them have been nowadayspractically utilized as an active ingredient in herbicidal compositions.However, there is a continuous demand for much more effective herbicidalcompounds in the art.

As a result of our earnest studies on pyrazole ring-containingsubstances and their herbicidal activities, we have found that thepyrazole derivatives having the above formula (I), the salts thereof andthe organic acid esters thereof show prominent herbicidal activities andalso that the pyrazole derivatives having the above for formula (II) arenew substances which have also herbicidal activities.

With respect the prior art found during the above-mentioned ourstudying, it is pointed out that only4-benzoyl-5-hydroxy-1,3-dimethylpyrazole and its utility as a chelatingagent are disclosed in Chemische Berichte, 106, 332-338 (1973) and alsothat synthesis of 1,3-dimethyl-4-(2-chlorobenzoyl)-5-hydroxypyrazole and1,3-dimethyl-4-(4-nitrobenzoyl)-5-hydroxypyrazole is briefly disclosedwithout any indication of their property, use, usage etc. in "TheChemistry of Heterocyclic Compounds" (Russian origin, 1972, No. 6,799-804).

Accordingly, it is a primary object of this invention to provide aneffective herbicidal composition containing a pyrazole derivative (I).

Another object of this invention is to provide a certain group of newpyrazole derivatives (II) having herbicidal activities.

Other objects and advantages of this invention will become apparent fromthe description given hereinbelow.

In one aspect of this invention, there is provided a herbicidalcomposition which comprises as an active ingredient a pyrazole compoundof the above formula (I), a salt thereof or an organic acid esterthereof and an agriculturally acceptable carrier.

Of the compounds having the above formula (I), preferable are thosewherein R₁ is hydrogen atom or an alkyl group of 1-6 carbon atoms, R₂ isan alkyl group of 1-6 carbon atoms or an alkenyl group of 3-6 carbonatoms, X is a halogen atom, nitro group, an alkyl group of 1-4 carbonatoms, a halogenated alkyl group of 1-2 carbon atoms and having 1-3halogen atoms, an alkoxy group of 1-4 carbon atoms, an alkanesulfonylgroup of 1-4 carbon atoms, cyano group, an alkylthio group of 1-4 carbonatoms, an alkanoyl group of 2-5 carbon atoms or an aliphatic acyl groupof 2-5 carbon atoms and n is an integer of 1-3 and when n is 2 or 3, X'smay be the same or different.

A more preferable group of the compounds having the above formula (I)includes those wherein R₁ is hydrogen atom or an alkyl group of 1-3carbon atoms, R₂ is an alkyl group of 1-3 carbon atoms or an alkenylgroup of 3 or 4 carbon atoms, X is a halogen atom, cyano group, nitrogroup, an alkyl group of 1-4 carbon atoms, an alkoxy group of 1-4 carbonatoms, an alkanesulfonyl group of 1-4 carbon atoms or trifluoromethylgroup and n is an integer of 1-3 and when n is 2 or 3, X's may be thesame or different.

A most preferable group of the compounds having the above formula (I)includes those wherein R₁ is methyl group, R₂ is methyl group or allylgroup, X is chlorine atom, nitro group, cyano group, methyl group,methoxy group, methanesulfonyl group or trifluoromethyl group and n isan integer of 1-3 and when n is 2 or 3, X's may be the same ordifferent, in view of their herbicidal activities.

Salts and organic acid esters of the compounds (I) may be advantageouslyemployed as an active ingredient in the present composition.Particularly preferable salts are those metal salts, ammonium salt andmineral acid salts as set forth above. Organic acids for particularlypreferable organic acid esters are those aliphatic, alicyclic oraromatic carboxylic acids, sulfonic acid, carbonic acid or thiocarbonicacid monoester and dibasic acids as set forth above.

More preferable organic acids are the carboxylic acid having the aboveformula wherein R₃ is a halogenoalkyl group of 1-2 carbon atoms and of1-4 halogen atoms, an alkenyl group of 3-5 carbon atoms, a 5- or6-membered cycloalkyl group, a phenyl group optionally having 1-3substituents of nitro, halogen and/or methyl, a phenylalkyl group of 1or 2 carbon atoms in the alkyl moiety and optionally having 1-3substituents of nitro and/or halogen in the phenyl moiety or aphenoxyalkyl group of 1 or 2 carbon atoms in the alkyl moiety andoptionally having 1 or 2 substituents of halogen and/or nitro; thesulfonic acids having the above formula wherein R₆ is an alkyl group of1-3 carbon atoms, a halogenoalkyl group of 1 or 2 carbon atoms and 1-3halogen atoms or a phenyl group optionally having C₁ or C₂ alkyl orhalogen; the monoesters of carbonic or thiocarbonic acid having theabove formula wherein R₈ is an alkyl group of 1-4 carbon atoms, phenylgroup or a phenylalkyl group of 1 or 2 carbon atoms in the alkyl moietyand optionally having 1 or 2 substituents of nitro and/or halogen in thephenyl moiety; and the dibasic acids having the above formula wherein R₉is an alkylene group of 1-3 carbon atoms and m is zero or 1.

The compounds having the above-mentioned formula (I) which may beemployed in the present herbicidal composition are illustrativelyexemplified as hereunder (Compound No. will be frequently referred tohereinbelow).

    ______________________________________                                        Compound No.                                                                            Compound                                                            ______________________________________                                        1.        1,3-dimethyl-4-(3-chlorobenzoyl)-5-                                           hydroxypyrazole                                                     2.        1,3-dimethyl-4-(4-chlorobenzoyl)-5-                                           hydroxypyrazole                                                     3.        1,3-dimethyl-4-(2-chlorobenzoyl)-5-                                           hydroxypyrazole                                                     4.        1,3-dimethyl-4-(3,4-dichlorobenzoyl)-5-                                       hydroxypyrazole                                                     5.        1,3-dimethyl-4-(4-methylbenzoyl)-5-                                           hydroxypyrazole                                                     6.        1,3-dimethyl-4-(3-methylbenzoyl)-5-                                           hydroxypyrazole                                                     7.        1,3-dimethyl-4-(3-trifluoromethylbenzoyl)-                                    5-hydroxypyrazole                                                   8.        1,3-dimethyl-4-(2-methoxybenzoyl)-5-                                          hydroxypyrazole                                                     9.        1,3-dimethyl-4-(4-nitrobenzoyl)-5-                                            hydroxypyrazole                                                     10.       1,3-dimethyl-4-(3-nitrobenzoyl)-5-                                            hydroxypyrazole                                                     11.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-                                       hydroxypyrazole                                                     12.       1,3-dimethyl-4-(3,5-dinitrobenzoyl)-5-                                        hydroxypyrazole                                                     13.       1,3-dimethyl-4-(4-bromobenzoyl)-5-                                            hydroxypyrazole                                                     14.       1,3-dimethyl-4-(2-nitro-4-chlorobenzoyl)-                                     5-hydroxypyrazole                                                   15.       1,3-dimethyl-4-(3,5-dichlorobenzoyl)-5-                                       hydroxypyrazole                                                     16.       1,3-dimethyl-4-(2-chlorobenzoyl)-5-                                           methoxycarbonyloxypyrazole                                          17.       1,3-dimethyl-4-(2-chlorobenzoyl)-5-                                           (N,N-dimethylcarbamoyloxy)pyrazole                                  18.       1,3-dimethyl-4-(2-chlorobenzoyl)-5-                                           acetoxypyrazole                                                     19.       1,3-dimethyl-4-(2-nitrobenzoyl)-5-                                            hydroxypyrazole                                                     20.       1,3-dimethyl-4-(3,4,5-trimethoxybenzoyl)-                                     5-hydroxypyrazole                                                   21.       1,3-dimethyl-4-(2-fluorobenzoyl)-5-                                           hydroxypyrazole                                                     22.       1,3-dimethyl-4-(2-bromobenzoyl)-5-                                            hydroxypyrazole                                                     23.       1,3-dimethyl-4-(2,5-dichlorobeonzyl)-5-                                       hydroxypyrazole                                                     24.       1,3-dimethyl-4-(4-methoxybenzoyl)-5-                                          hydroxypyrazole                                                     25.       1,3-dimethyl-4-(methylthiobenzoyl)-5-                                         hydroxypyrazole                                                     26.       1,3-dimethyl-4-(3,4-dimethoxybenzoyl)-5-                                      hydroxypyrazole                                                     27.       1,3-dimethyl-4-(4-tert.-butylbenzoyl)-                                        5-hydroxypyrazole                                                   28.       1,3-dimethyl-4-(3,4-dimethylbenzoyl)-                                         5-hydroxypyrazole                                                   29.       1,3-dimethyl-4-(3,5-dimethylbenzoyl)-                                         5-hydroxypyrazole                                                   30.       bis[1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-                                   pyrazolyl]sebacate                                                  31.       bis[1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                     5-pyrazolyl]maleate                                                 32.       1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-                                     5-hydroxypyrazole                                                   33.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-(4-methylbenzoyloxy)pyrazole                                      34.       1-methyl-3-n-propyl-4-(2-chlorobenzoyl)-                                      5-hydroxypyrazole                                                   35.       1-methyl-4-(2-chlorobenzoyl)-5-hydroxy-                                       pyrazole                                                            36.       1,3-dimethyl-4-(3,5-dimethoxybenzoyl)-                                        5-hydroxypyrazole                                                   37.       1-methyl-3-ethyl-4-(2,4-dichlorobenzoyl)-                                     5-hydroxypyrazole                                                   38.       1,3-dimethyl-4-(2-nitro-5-methylbenzoyl)-                                     5-hydroxypyrazole                                                   39.       1,3-dimethyl-4-(4-methanesulfonylbenzoyl)-                                    5-hydroxypyrazole                                                   40.       1-isopropyl-3-methyl-4-(2-chlorobenzoyl)-                                     5-hydroxypyrazole                                                   41.       1,3-dimethyl-4-(2-iodobenzoyl)-5-                                             hydroxypyrazole                                                     42.       1,3-dimethyl-4-(4-fluorobenzoyl)-5-                                           hydroxypyrazole                                                     43.       1,3-dimethyl-4-(4-cyanobenzoyl)-5-                                            hydroxypyrazole                                                     44.       1-ethyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-hydroxypyrazole                                                   45.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-                                       lauroyloxypyrazole                                                  46.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-stearoyloxypyrazole                                               47.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-crotonyloxypyrazole                                               48.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-benzoyloxypyrazole                                                49.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-pyrazolyl methanesulfonate                                        50.       1,3-dimethyl-4-(2-chloro-4-cyanobenzoyl)-                                     5-hydroxypyrazole                                                   51.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-pyrazolyl 4-toluenesulfonate                                      52.       1,3-dimethyl-4-(2-acetylbenzoyl)-5-                                           hydroxypyrazole                                                     53.       1,3-dimethyl-4-(2,4,5-trichlorobenzoyl)-                                      5-hydroxypyrazole                                                   54.       1,3-dimethyl-4-(2,3,4,5-tetrachlorobenzoyl)-                                  5-hydroxypyrazole                                                   55.       bis[1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-                                 5-pyrazolyl]terephthalate                                           56.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-acetoxypyrazole                                                   57.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-propionyloxypyrazole                                              58.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-isobutyryloxypyrazole                                             59.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-(5-methyl-3-oxo-4-isoxazolin-2-                                             ylcarbonyloxy)pyrazole                                              60.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-(3-oxo-4-chloro-5-methyl-4-isoxazolin-                                      2-ylcarbonyloxy)-pyrazole                                           61.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-hydroxypyrazole hydrochloride                                     62.       1,3-dimethyl-4-(2,3-dichloro-4-nitrobenzoyl)-                                 5-hydroxypyrazole                                                   63.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-methoxycarbonyloxypyrazole                                        64.       1,3-dimethyl-4-(3,4-dichlorobenzoyl)-                                         5-n-propoxycarbonyloxypyrazole                                      65.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-benzyloxycarbonyloxypyrazole                                      66.       bis[1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                     5-pyrazoly]carbonate                                                67.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-hydroxypyrazole calcium salt                                      68.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-hydroxypyrazole magnesium salt                                    69.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-hydroxypyrazole isopropylamine salt                               70.       1,3-dimethyl-4-(2,4-dichloro-5-methyl-                                        benzoyl)-5-hydroxypyrazole                                          71.       1,3-dimethyl-4-(3,4-dimethoxybenzoyl)-5-                                      hydroxypyrazole hydrochloride                                       72.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-phenoxycarbonyloxypyrazole                                        73.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-linoleyloxypyrazole                                               74.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-chloroacetoxypyrazole                                             75.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-                                       (2-methyl-4-chlorophenoxyacetoxy)pyrazole                           76.       1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-                                     5-benzoyloxypyrazole                                                77.       1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-                                     5-(4-chlorobenzoyloxy)pyrazole                                      78.       1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-                                     5-(2-chloro-4-nitrobenzoyloxy)pyrazole                              79.       1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-                                     5-cinnamoyloxypyrazole                                              80.       bis[1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-                                 5-pyrazolyl]succinate                                               81.       1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-                                     5-acetoxypyrazole                                                   82.       1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-                                     5-pivaloyloxypyrazole                                               83.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-pivaloyloxypyrazole                                               84.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-phenylthiocarbonyloxypyrazole                                     85.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-n-butylthiocarbonyloxypyrazole                                    86.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-phenylacetoxypyrazole                                             87.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-(4-chlorophenylacetoxy)pyrazole                                   88.       1,3-dimethyl-4-(3-methyl-4-nitrobenzoyl)-                                     5-hydroxypyrazole                                                   89.       1,3-dimethyl-4-(2-chloro-4-nitro-5-methyl-                                    benzoyl)-5-hydroxypyrazole                                          90.       1,3-dimethyl-4-(2-methylbenzoyl)-5-                                           hydroxypyrazole                                                     91.       1,3-dimethyl-4-(2,4-dimethylbenzoyl)-                                         5-hydroxypyrazole                                                   92.       1,3-dimethyl-4-(2,6-dichlorobenzoyl)-                                         5-hydroxypyrazole                                                   93.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-pyrazolyl 4-chlorobenzenesulfonate                                94.       1,3-dimethyl-4-(4-nitrobenzoyl)-5-                                            acetoxypyrazole                                                     95.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-cyclohexylcarbonyloxypyrazole                                     96.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-(2,4-dichlorophenoxyacetoxy)pyrazole                              97.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-                                       (2,4-dichlorobenzoyloxy)pyrazole                                    98.       O,O-diethyl O-[1,3-dimethyl-4-(2-chloro-                                      benzoyl)-5-pyrazolyl]phosphorothioate                               99.       1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-pyrazolyl chloromethanesulfonate                                  100.      1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-hydroxypyrazole aluminum salt                                     101.      1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-hydroxypyrazole iron salt                                         102.      1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-hydroxypyrazole copper salt                                       103.      1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-hydroxypyrazole sodium salt                                       104.      1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-pyrazolyl benzenesulfonate                                        105.      1,3-dimethyl-4-(2-nitro-4-chlorobenzoyl)-                                     5-pyrazolyl 4-toluenesulfonate                                      106.      1,3-dimethyl-4-(2-nitro-4-chlorobenzoyl)-                                     5-pyrazolyl benzenesulfonate                                        107.      1-ethyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-pyrazolyl 4-toluenesulfonate                                      108.      1-ethyl-3-methyl-4-(2-nitro-4-chloro-                                         benzoyl)-5-hydroxypyrazole                                          109.      1-ethyl-3-methyl-4-(2-nitro-4-chloro-                                         benzoyl)-5-pyrazolyl 4-toluenesulfonate                             110.      1,3-dimethyl-4-(2-chlorobenzoyl)-5-                                           pyrazolyl methanesulfonate                                          111.      1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-ethylthiocarbonyloxypyrazole                                      112.      1,3-dimethyl-4-(2,4-dichlorobenzoyl)-                                         5-benzylthiocarbonyloxypyrazole                                     113.      1-allyl-3-methyl-4-(4-chlorobenzoyl)-                                         5-hydroxypyrazole                                                   114.      1-allyl-3-methyl-4-(2-chlorobenzoyl)-5-                                       hydroxypyrazole                                                     115.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-(4-chlorobenzoyloxy)pyrazole                                      116.      1-(2-hexenyl)-3-methyl-4-(4-bromobenzoyl)-                                    5-hydroxypyrazole                                                   117.      1-(3-methyl-2-butenyl)-3-methyl-4-(2-                                         nitro-4-chlorobenzoyl)-5-hydroxypyrazole                            118.      1-(3-pentenyl)-3-methyl-4-(2-chloro-                                          benzoyl)-5-methoxycarbonyloxypyrazole                               119.      1-allyl-3-methyl-4-(2-chlorobenzoyl)-                                         5-(N,N-dimethylcarbamoyloxy)pyrazole                                120.      1-allyl-3-methyl-4-(2-chlorobenzoyl)-                                         5-acetoxypyrazole                                                   121.      1-(2-methyl-2-propenyl)-3-methyl-4-(2-                                        fluorobenzoyl)-5-hydroxypyrazole                                    122.      1-(2-butenyl)-3-methyl-4-(2-bromobenzoyl)-                                    5-hydroxypyrazole                                                   123.      bis[1-allyl-3-methyl-4-(2,4-dichloro-                                         benzoyl)-5-pyrazolyl]sebacate                                       124.      bis[1-allyl-3-methyl-4-(2,4-dichloro-                                         benzoyl)-5-pyrazolyl]maleate                                        125.      1-allyl-3-methyl-4-(2-chloro-4-nitro-                                         benozyl)-5-pyrazolyl-4-toluenesulfonate                             126.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-(4-methylbenzoyloxy)pyrazole                                      127.      1-allyl-4-(2-chlorobenzoyl)-5-hydroxy-                                        pyrazole                                                            128.      1-allyl-3-ethyl-4-(2-chlorobenzoyl)-                                          5-hydroxypyrazole                                                   129.      1-(2-butenyl)-3-methyl-4-(2-iodobenzoyl)-                                     5-hydroxypyrazole                                                   130.      1-(1-methyl-2-butenyl)-3-methyl-4-(4-                                         fluorobenzoyl)-5-hydroxypyrazole                                    131.      1-(2-butenyl)-3-methyl-4-(2,4-dichloro-                                       benzoyl)-5-hydroxypyrazole                                          132.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-lauroxyloxypyrazole                                               133.      1-allyl-3-n-propyl-4-(2,4-dichlorobenzoyl)-                                   5-benzoyloxypyrazole                                                134.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-pyrazolyl methanesulfonate                                        135.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-pyrazolyl 4-toluenesulfonate                                      136.      1-(2-butenyl)-3-methyl-4-(2,4,5-trichloro-                                    benzoyl)-5-hydroxypyrazole                                          137.      1-allyl-3-methyl-4-(2,3,4,5-tetrachloro-                                      benzoyl-5-hydroxypyrazole                                           138.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-(4-nitrobenzyloxycarbonyloxy)pyrazole                             139.      bis[1-allyl-3-methyl-4-(2-chloro-4-                                           nitrobenzoyl)-5-pyrazolyl]terephthalate                             140.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-propionyloxypyrazole                                              141.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-isobutylyloxypyrazole                                             142.      1-(2-methyl-2-propenyl)-3-methyl-4-                                           (2,4-dichlorobenzoyl)-5-(5-methyl-3-oxo-                                      4-isoxazolin-2-ylcarbonyloxy)pyrazole                               143.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-(3-oxo-4-chloro-5-methyl-4-isoxazolin-                                      2-ylcarbonyloxy)pyrazole                                            144.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-hydroxypyrazole hydrochloride                                     145.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-methoxycarbonyloxypyrazole                                        146.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-n-propoxycarbonyloxypyrazole                                      147.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-benzyloxycarbonyloxypyrazole                                      148.      bis[1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                 5-pyrazolyl]carbonate                                               149.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-hydroxypyrazole calcium salt                                      150.      1-(2-methyl-2-propenyl)-3-methyl-4-(2,4-                                      dichlorobenzoyl)-5-hydroxypyrazole                                            magnesium salt                                                      151.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-hydroxypyrazole isopropylamine salt                               152.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-linoleyloxypyrazole                                               153.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-chloroacetoxypyrazole                                             154.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-(2-methyl-4-chlorophenoxyacetoxy)pyrazole                         155.      1-(2-methyl-2-propenyl)-3-methyl-4-(2-                                        chloro-4-nitrobenzoyl)-5-benzoyloxypyrazole                         156.      1-allyl-3-methyl-4-(2-chloro-4-nitro                                          benzoyl)-5-(4-chlorobenzoyloxy)pyrazole                             157.      1-allyl-3-methyl-4-(2-chloro-4-nitro-                                         benzoyl)-5-cinnamoyloxypyrazole                                     158.      bis[1-allyl-3-methyl-4-(2-chloro-4-                                           nitrobenzoyl)-5-pyrazolyl]succinate                                 159.      1-allyl-3-methyl-4-(2-chloro-4-nitro-                                         benzoyl)-5-pivaloyloxypyrazole                                      160.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-pivaloyloxypyrazole                                               161.      1-(2-methyl-2-propenyl)-3-methyl-4-(2,4-                                      dichlorobenzoyl)-5-phenylthiocarbonyloxy-                                     pyrazole                                                            162.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-n-butylthiocarbonyloxypyrazole                                    163.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-phenylacetoxypyrazole                                             164.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-(4-chlorophenylacetoxy)pyrazole                                   165.      1-allyl-3-methyl-4-(2,6-dichlorobenzoyl)-                                     5-hydroxypyrazole                                                   166.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-pyrazolyl 4-chlorobenzenesulfonate                                167.      1-(1-methyl-2-propenyl)-3-methyl-4-(4-                                        nitrobenzoyl)-5-acetoxypyrazole                                     168.      1-(2-butenyl)-3-methyl-4-(2,4-dichloro-                                       benzoyl)-5-(2,4-dichlorobenzoyloxy)                                           pyrazole                                                            169.      O,O-diethyl[O- 1-allyl-3-methyl-4-(2-                                         chlorobenzoyl)-5-pyrazolyl]phosphorothioate                         170.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-pyrazolyl chloromethanesulfonate                                  171.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-hydroxypyrazole aluminum salt                                     172.      1-(2-methyl-2-propenyl)-3-methyl-4-(2,4-                                      dichlorobenzoyl)-5-hydroxypyrazole iron                                       salt                                                                173.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-hydroxypyrazole copper salt                                       174.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-hydroxypyrazole sodium salt                                       175.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-pyrazolyl benzenesulfonate                                        176.      1-allyl-3-methyl-4-(2-nitro-4-chloro-                                         benzoyl)-5-pyrazolyl 4-toluenesulfonate                             177.      1-(2-butenyl)-3-methyl-4-(2-nitro-4-                                          chlorobenzoyl)-5-pyrazolyl benzenesulfonate                         178.      1-allyl-3-methyl-4-(2-nitro-4-chloro-                                         benzoyl)-5-hydroxypyrazole                                          179.      1-allyl-4-(2-nitro-4-chlorobenzoyl)-5-                                        pyrazolyl 4-toluenesulfonate                                        180.      1-(2-hexenyl)-3-methyl-4-(2-chlorobenzoyl)-                                   6-pyrazolyl methanesulfonate                                        181.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-ethylthiocarbonyloxypyrazole                                      182.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-benzylthiocarbonyloxypyrazole                                     183.      1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-                                     5-hydroxypyrazole                                                   184.      1-allyl-3-methyl-4-(3-chlorobenzoyl)-5-                                       stearoyloxypyrazole                                                 185.      1-(3-butenyl)-3-methyl-4-(3,4-dichloro-                                       benzoyl)-5-crotonyloxypyrazole                                      186.      1-allyl-3-methyl-4-(3-nitrobenzoyl)-5-                                        hydroxypyrazole                                                     187.      1-allyl-3-methyl-4-(3,5-dinitrobenzoyl)-                                      5-phenoxycarbonyloxypyrazole                                        188.      1-allyl-3-methyl-4-(4-bromobenzoyl)-                                          5-(2-chloro-4-nitrobenzoyloxy)pyrazole                              189.      1-(3-butenyl)-3-methyl-4-(3,5-dichloro-                                       benzoyl)-5-hydroxypyrazole                                          190.      1-allyl-5-methyl-4-(2-nitrobenzoyl)-5-                                        pyrazolyl 4-toluenesulfonate                                        191.      1-allyl-3-methyl-4-(2,5-dichlorobenzoyl)-                                     5-(3,4-dichlorophenoxyacetoxy)pyrazole                              192.      1-allyl-3-methyl-4-(2,3-dichloro-4-                                           nitrobenzoyl)-5-cyclohexylcarbonyl-                                           oxypyrazole                                                         ______________________________________                                    

Of the above-illustrated pyrazole compounds, may be mentioned as apreferable class those compounds having the Compound Nos. 11, 14, 19,22, 23, 26, 32, 33, 35, 38, 39, 41, 44, 45, 46, 47, 48, 49, 51, 56, 57,58, 59, 60, 61, 63, 64, 65, 67, 68, 69, 72, 73, 74, 80, 83, 84, 85, 86,90, 96, 97, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 111, 125,141 and 183.

The compounds having the above formula (I), salts thereof and organicacid esters thereof can be readily prepared, for example, by thefollowing processes.

(Process A) The 5-hydroxypyrazole derivatives (I) can be easily preparedby reacting the 5-pyrazolone derivatives (VI) with the acyl halides(VII) in the presence of a catalyst as shown by the following equation.##STR12## (wherein R₁, R₂, X and n have the same meanings as above andHal means a halogen atom.)

The above reaction may be preferably effected in the presence of asolvent. As the solvent employable, any solvent may be used withoutparticular limitation if it could not participate in the reaction andthere may be mentioned, for instance, ethers or mixtures thereof such asdiethylether, tetrahydrofuran, diethylether-dioxane,tetrahydrofuran-dioxane; halogenated hydrocarbons such asdichloromethane, carbon tetrachloride; secondary or tertiary alcoholssuch as isopropanol, isobutanol, tert.-butanol; and the like. Inparticular, ethers and secondary alcohols are preferably employed. Thereaction may also be preferably effected in the presence of a catalyst.As the catalyst to be used are mentioned alkaline earth metal hydroxidessuch as calcium hydroxide. In particular, calcium hydroxide ispreferably used. The amount of a catalyst to be employed is preferably1-2 moles per mole of the starting material (VI). The reactiontemperature is not particularly critical and the reaction may beeffected at room temperature or a reflux temperature of the solventemployed. Particularly, the reaction may be preferably conducted at areflux temperature of the solvent employed. The reaction period may varymainly upon the reaction temperature and the sort of the reagentemployed, but is is usually within a range of about 1 to 10 hours. And,the acyl halides which may be employed in the above-mentioned reactionmay be, for example, acid chlorides or acid bromides.

After completion of the reaction, the desired compounds may be recoveredfrom the reaction mixture by a conventional method. And, the startingmaterials of the formula (VI) are prepared according to the methoddisclosed in Chemische Berichte, 43, 2106 (1910).

(Process B) The compounds having the formula (I) are obtainable byheating the corresponding 5-halogenopyrazole derivatives (VIII) withalkali metal hydrosulfides such as sodium hydrosulfide or alkali metalhydroxides such as sodium hydroxide or potassium hydroxide. ##STR13##(wherein R₁, R₂, X, and n have the same meanings as above.)

In the above-mentioned reaction, water may be employed as a solvent.And, a mixture of water with an organic solvent may be used and, asexamples of such organic solvents, may be mentioned ethers such astetrahydrofuran, dioxane; alcohols such as methanol, ethanol. Thereaction temperature is not particularly critical and the reaction maybe effected at room temperature or a reflux temperature of the solventand, particularly, it can be preferably effected at a temperature aroundthe reflux temperature of the solvent. The reaction period may varymainly upon the reaction temperature and the sort of the reagentemployed, but usually about 1 to 10 hours. And, the starting materialsof the formula (VIII) are prepared according to the method disclosed inChemische Berichte, 50, 737 (1917) and United Kingdom PatentSpecification No. 1268608.

(Process C) The organic acid esters of the compounds having the formula(I) are easily prepared by reacting the compounds of the formula (I)with an acylating agent as shown in the following schema. ##STR14##(wherein R₁, R₂, X, and n have the same meanings as above and R₁₁represents a residue of an organic acid.)

The above-mentioned reaction may be preferably effected in the presenceof a solvent. As the solvent which may be employed, there is noparticular limitation thereon if it does not participate in the presentreaction and, for example, ethers or mixtures thereof such as diethylether, tetrahydrofuran, diethyl ether-dioxane, tetrahydrofurandioxane;aromatic hydrocarbons such as benzene, toluene, xylene; halogenatedhydrocarbons such as dichloromethane, chloroform, carbon tetrachlorideand, in particular, the aromatic hydrocarbons and ethers are preferablyemployed. And, the acylating agents which may be employed are acylhalides such as acid chlorides and acid bromides; carboxylic acids inthe presence of carbodiimides such as 1,3-dicyclohexylcarbodiimide; oracid anhydrides and acid chlorides are preferable and the reaction iseffected in the presence of an acid binding agent. The reactiontemperature is not particularly critical and the reaction is usuallyconducted at room temperature to a reflux temperature of the solvent.The reaction period may vary mainly upon the reaction temperature, thesort of the reagent etc., but usually about 1-24 hours.

(Process D) The salts of the compound having the formula (I) with ametallic ion, a complex ion and ammonium ion are formed by adjusting apH of a solution of the compound of the formula (I) to not less thanabout 3 in the presence of a cation. As the solvent which may be usedfor the formation of the above-mentioned salts, there is no particularlimitation and, for instance, are preferably employed water; alcoholssuch as methanol or ethanol; ethers such as tetrahydrofuran or dioxane;aromatic hydrocarbons such as benzene; halogenated hydrocarbons such asdichloromethane or chloroform or mixture of these organic solvents withwater. Depending upon changes in cation valency and solvent, varioussalts having different coordinate proportions of the compound having theformula (I) and the cation of 1:1, 1:2, 1:3 and the like are formed.

(Process E) The salts of the compound having the formula (I) and amineral acid are easily prepared by mixing the compound having theformula (I) with the mineral acid in a suitable solvent. As the solventwhich may be used, there is no particular limitation and there may bepreferably mentioned, for instance, water; alcohols such as methanol orethanol; ethers such as tetrahydrofuran or dioxane; aromatichydrocarbons such as benzene; halogenated hydrocarbons such asdichloromethane or chloroform; or mixtures of these organic solvent andwater. In general, the salts with the mineral acid are formed at a pHnot more than about 3 of the solution.

The compounds of the above-mentioned formula (I), salts thereof andorganic acid esters thereof are utilized as herbicides and have aproperty of killing weeds by causing chlorosis.

In a paddy field, particularly prominent herbicidal effects againstperennial weeds such as those of the family Cyperaceae, for example,"Hotauri" (Scirpus hotauri Ohwi.), "Mizugayatsuri" (Cyperus serotinusRottb.) and the like and those of the family Alismataceae, for example,"Omodaka" (Sagittaria trifolia L.), "Urikawa" (Sagittaria pygmaea Miq.),which are difficult to be controlled by usual herbicides, can beachieved by pre- and post-emergency treatment in soil without anyharmful effect on transplanted rice plants and growing rice plants and,furthermore, monocotyledonous weeds such as those of the familyGramineae, for example, barnyardgrass, panic grass and the like andbroad-leaf weeds such as those of the family Scrophulariaceae, forexample, false pimpernel, "Murasakisagigoke" (Mazus miquelii Makino),"Abunome" (Dopatrium junceum Hamilt.) and the like, those of the familyCruciferae, for example, wavy bittercress, marsh yellow cress,"Mizutagarashi" (Cardamine lyrate Bunge) and the like, those of thefamily Lythraceae, for example, toothcup, "Mizumatsuba" (Rotala mexicanaCham.) and the like and those of the family Compositae, for example,ragwort, American false daisy and the like.

In an upland field, pre- and post-emergency treatment in soils showsparticularly prominent effect against weeds of the familyCaryophyllaceae, for example, common chickweed, Bog stichwort, mouse-earchickweed, pearlwort and the like and, furthermore, broad-leaf weedssuch as those of the family Portulacaceae, for example, common purslaneand the like, those of the family Amaranthaceae, for example, pigweed,rough pigweed and the like, those of the family Chenopodiaceae, forexample, "Akaza" (Chenopodium album L.), common lamb's-quarters,"Koakaza" (C. ficifolium Smith) and the like, those of the familyCommelinaceae, for example, asatic dayflower and the like, those of thefamily Labiatae, for example, henbit, "Kiranso" (Ajuga decumbens Thunb.)and the like, those of the family Oxalidaceae, for example, creepingwood sorrel, violet wood sorrel and the like, those of the familyLeguminosae, for example, "Nekohagi" (Lespedeza pilosa Sieb et Zucc.),hairy vetch, common vetch and the like, those of the familyEuphorbiaceae, for example, Virginia coperleaf, milk purslane and thelike can be effectively controlled. And, narrow-leaf weeds, inparticular, those of the family Cyperaceae, such as "Kayatsurigusa"(Cyperus microiria Steud.) and the like are effectively controlled andthose of the family Gramineae such as wheatgrass, crab-grass,"Komehishiba" (Digitaria timorensis Balansa), barnyardgrass, greenfoxtail, "Akinoenokorogusa" (Setaria Faberi Herrmann), foxtail and thelike are also effectively controlled. On the other hand, crops such asrice plants, corns, sugar beets, soybeans, cotton plants, radishes,tomatoes, carrots, Chinese cabbages, lettuces and the like do not sufferfrom phytotoxicity.

Additionally, the compounds having the above-mentioned formula (I) areeffectively usable as herbicides in an orchard, a non-crop land, aforest and so on.

The compounds in this invention may be formulated for use to thepreparations commonly employed as a herbicide, for example, powderydusts, coarse dusts, fine granules, granules, wettabble powders,emulsifiable concentrates, aqueous liquids, water soluble powders, oilsuspensions and so on, with admixture of a carrier and, if required,other auxilliary agents. The carrier as used herein means a synthetic ornatural and inorganic or organic substance that is mixed with on activecompound and can assist an active compound in its arrival to the portionto be treated and make it easy to store, transport or handle.

As suitable solid carriers may be mentioned inorganic substances such asclays, which may be represented by Kaolinite, Montmorillonite orAttapulgite, talc, mica, pyrophyllite, pumice, vermiculite, gypsum,calcium carbonate, dolomite, diatomaceous earth, magnesium carbonate,apatite, zeolite, silicic anhydride, synthetic calcium silicate and thelike, vegetable organic substances such as soybean meal, tobacco powder,walnut powder, wheat flour, wood meal, starch, crystalline cellulose andthe like, synthetic or natural high polymer compounds such as cumaroneresin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkyleneglycol, ketone resin, ester gum, copal gum, dammar gum, and the like,waxes such as carnauba wax, beeswax and the like or urea.

As suitable liquid media or carriers may be mentioned paraffin ornaphthene hydrocarbons such as kerosine, mineral oil, spindle oil, whiteoil and the like, aromatic hydrocarbons such as benzene, toluene,xylene, ethylbenzene, cumene, methylnaphthalene and the like,chlorinated hydrocarbons such as carbon tetrachloride, chloroform,trichloroethylene, monochlorobenzene, o-chlorotoluene and the like,ethers such as dioxane, tetrahydrofuran and the like, ketones such asacetone, methylethylketone, diisobutylketone, cyclohexanone,acetophenone, isophorone and the like, esters such as ethyl acetate,amyl acetate, ethylene glycol acetate, diethylene glycol acetate,dibutyl maleate, diethyl succinate and the like, alcohols such asmethanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol,benzyl alcohol and the like, ether alcohols such as ethylene glycolethyl ether, ethylene glycol phenyl ether, diethylene glycol ethylether, diethylene glycol butyl ether and the like, polar solvents suchas dimethylformamide, dimethylsulfoxide and the like or water.

As the surface active agents used for emulsifying, dispersing, wetting,spreading, binding, controlling disintegration, stabilizing activeingredient, improving fruidity, rust proofing and so on may be utilizedany of non-ionic, anionic, cationic and amphoteric ones, but non-ionicand/or anionic agents are usually employed. As suitable non-ionicsurface active agents may be mentioned, for example, polymerizationadducts of ethylene oxide to higher alcohols such as lauryl alcohol,stearyl alcohol, oleyl alcohol and the like, polymerization adducts ofethylene oxide to alkyl phenols such as isooctyl phenol, nonyl phenoland the like, polymerization adducts of ethylene oxide to alkylnaphthols such as butyl naphthol, octyl naphthol and the like,polymerization adducts of ethylene oxide to higher fatty acids such aspalmitic acid, stearic acid, oleic acid and the like, polymerizationadducts of ethylene oxide to mono- or di-alkyl phosphoric acids such asstearyl phosphoric acid, dilauryl phosphoric acid and the like,polymerization adducts of ethylene oxide to amines such as dodecylamine, stearic acid amide and the like, polymerization adducts ofethylene oxide to higher fatty acid esters of polyhydric alcohols suchas sorbitan and said fatty acid esters, polymerization adducts ofethylene oxide to propylene oxide and so on. As suitable anionic surfaceactive agents may be mentioned, for example, alkyl sulfate salts such assodium lauryl sulfate, oleyl sulfate amine salt and the like, alkylsulfonate salts such as sodium dioctyl sulfosuccinate, sodium2-ethylhexene sulfonate and the like, aryl sulfonate salts such assodium isopropylnaphthalene sulfonate, sodium methylenebisnaphthalenesulfonate, sodium ligninsulfonate, sodium dodecylbenzene sulfonate andthe like.

Moreover, the herbicidal compositions of this invention may be used incombination with high molecular compounds or other auxiliary agents suchas casein, gelatin, albmin, glue, sodium alginate, carboxymethylcellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcoholand the like for improving properties and increasing biological effectsthereof.

The above-mentioned carriers and various auxiliary agents may beoptionally utilized alone or in combination therewith for desiredpurposes, with consideration for the type of a preparation, applicationand other factors.

In general, the herbicidal composition of this invention may contain theactive compound (I) in an amount of 0.1-99% by weight, based upon thecomposition.

Dusts usually contain, for example, 1 to 25 parts by weight of theactive compound and the remainder is a solid carrier.

Wettable powders usually contain, for example, 25-90 parts by weight ofthe active compound and the remainder is a solid carrier and adispersing and wetting agent, if required, together with a protectivecolloidal agent, a thixotropic agent, an anti-foaming agent and thelike.

Granules usually contain 1-35 parts by weight of the active compound anda major portion of the remainder is a solid carrier. The active compoundis homogeneously admixed with the solid carrier or adhered or adsorbedon the carrier surface and the size of a granule is about 0.2-1.5 mm.

Emulsifiable concentrates usually contain, for example, 5-50 parts byweight of the active compound and about 5-20 parts by weight of anemulsifying agent, the remainder being a liquid carrier, if required,together with a corrosive inhibitor.

The herbicidal compositions of this invention, which are formulated intovarious types of preparations as above, may be applied in a paddy orupland field at 10-2000 g, preferably 100-500 g of the active ingredientper 10 a. for pre- or post-emergency soil treatment to control weedseffectively. Also, weeds can be unselectively controlled in non-cropland such as road, ground, house site, railroad and the like, at anapplication rate of the active ingredient of 200-4000 g per 10 a.

The herbicidal compositions of this invention may be preferably combinedwith other herbicides for broader herbicidal spectra and, in some cases,a synergistic effect is expectable. As examples of such other herbicidesmay be mentioned, for instance, triazine type herbicides such as2-methylthio-4,6-bisethylamino-1,3,5-triazine;2-chloro-4,6-bisethylamino-1,3,5-triazine;2-methoxy-4-ethylamino-6-isopropylamino-1,3,5-triazine;2-chloro-4-ethylamino-6-isopropylamino-s-triazine;2-methylthio-4,6-bis(isopropylamino)-s-triazine;2-methylthio-4-ethylamino-6-isopropylamino-s-triazine and the like,phenoxy type herbicides such as 2,4-dichlorophenoxyacetic acid and itsmethyl, ethyl or butyl ester; 2-chloro-4-methylphenoxyacetic acid;4-chloro-2-methylphenoxyacetic acid, ethyl2-methyl-4-chlorophenoxybutyrate and the like, diphenyl ether typeherbicides such as 2,4,6-trichlorophenyl-4'-nitrophenyl ether;2,4-dichlorophenyl-4'-nitrophenyl ether;3,5-dimethylphenyl-4'-nitrophenyl ether and the like, urea typeherbicides such as 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea;3-(3,4-dichlorophenyl)-1,1-dimethylurea;3-(4-chlorophenyl)-1,1-dimethylurea and the like, carbamate typeherbicides such as3-methoxycarbonylaminophenyl-N-(3-methylphenyl)carbamate; isopropylN-(3-chlorophenyl)carbamate; methyl N-(3,4-dichlorophenyl)carbamate andthe like, uracil type herbicides such as5-bromo-3-sec-butyl-6-methyluracil; 1-cyclohexyl-3,5-propyleneuracil andthe like, thiolcarbamate type herbicides such asS-(4-chlorobenzyl)-N,N-diethylthiolcarbamate; S-ethylN-cyclohexyl-N-ethylthiol carbamate;S-ethyl-hexahydro-1H-azepine-1-carbothioate;S-ethyl-N,N-di-n-propylthiocarbamate and the like, pyridinium salt typeherbicides such as 1,1'-dimethyl-4,4'-bispyridinium dichloride and thelike, phosphorus type herbicides such as N-(phosphonomethyl)glycine andthe like, aniline type herbicides such asα,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine;4-(methylsulfonyl)-2,6-dinitro-N,N-dipropylaniline and the like, acidanilide type herbicides such as2-chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide;2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide;3,4-dichloropropionanilide and the like,5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)1,3,4-oxadiazolin-2-one;2-[N-isopropyl-N-(4-chlorophenyl)-carbamoyl]-4-chloro-5-methyl-4-isoxazolin-3-one;3-isopropylbenzo-2-thia-1,3-diazinon-(4)-2,2-dioxide;3-(2-methylphenoxy)pyridazine and the like, but they are not critical.

The herbicidal compositions of this invention may be also applied withadmixture of plant growth regulators such as sodium naphthyl acetate;1,2-dihydropyridazine-3,6-dione; gibberellins and the like, fungicidessuch as methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate;1,2-bis(3-methoxycarbonyl-2-thioureido)benzene;3-hydroxy-5-methylisoxazole; N-2,3-dichlorophenyltetrachlorophthalamicacid; 5-methyl s-triazolo-(3,4-b)-benzthiazole;O,O-diisopropyl-S-benzylphosphorothioate; pentachloronitrobenzene;Kasugamycin; brasticidin S; 4,5,6,7-tetrachlorophthalide and the like,insecticides such as O,O-diethylO-(2-isopropyl-4-methyl-6-pyrimidinyl)phosphorothioate; O,O-diethylS-2-[(ethylthio)ethyl]phosphorodithioate; 1-naphthyl N-methylcarbamate;O,O-dimethyl O-(3-methyl-4-nitrophenyl)thiophosphate; O,O-dimethylS-(N-methylcarbamoylmethyl)phosphorodithioate;S-methyl-N-[(methylcarbamoyl)oxy]thioacetimidate; O,O-dimethylS-(N-methyl-N-formylcarbamoylmethyl)phosphorodithioate, O,O-dimethylS-2-(ethylthio)ethylphosphorodithioate; O,O-diethylS-2-[(ethylthio)ethyl]phosphorodithioate;O,O-dimethyl-1-hydroxy-2,2,2-trichloroethylphosphonate and the like orfertilizers and so on.

In another aspect of this invention, there is provided a new class ofthe pyrazole compounds having the above formula (II) which also showherbicidal activities as seen with respect to the compounds having theabove formula (I).

As a result of our further studying upon the finding previouslyexplained herein, we have also found that other particular new pyrazolecompounds, which are out of the scope of the compounds (I) including twoknown ones and defined by the above formula (II), have also considerableherbicidal activities, though not so prominent as in the compounds (I).

In view of this finding, the processes for the preparation of thecompounds (II), the application thereof as a herbicide etc. are thesubstantially same as in the case of the compounds (I), but there may bementioned the following compounds for the purpose of illustration only,in addition to those listed hereinabove with regard to the compounds(I):

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-mercaptopyrazole, m.p. 85°-86° C.

1,3-dimethyl-4-(4-benzoylbenzoyl)-5-hydroxypyrazole, m.p. 194°-195° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-acetylthiopyrazole. n_(D) ¹⁷.51.5890

moreover, the most preferable group of the compounds having the aboveformula (II) is the same as in the compounds (I).

In the preparation of the compounds having the above formula (II)wherein Y is sulfur atom, it is practically suitable to employ the aboveProcess B by the use of an alkali metal hydrosulfide instead of thealkali metal hydroxide.

The organic acid esters and salts of the compounds (II) may be readilyprepared from the corresponding free compounds according to the aboveProcesses C, D and E.

The preparation of the compound having the above formula (I) or (II) andthe herbicidal composition containing the compound having the aboveformula (I) will be more fully illustrated by way of the followingexamples.

EXAMPLE 1 1,3-Dimethyl-4-(4-nitrobenzoyl)-5-hydroxypyrazole

In 22 ml. of dry dioxane is dissolved 2.24 g. of1,3-dimethyl-5-pyrazolone and then 2.96 g. of calcium hydroxide is addedthereto. 3.71 g. of p-nitrobenzoyl chloride is added dropwise theretowhile stirring at room temperature. After completion of the dropwiseaddition, the mixture is heated under reflux for 1 hour. Aftercompletion of the reaction, the reaction mixture is allowed to cool andthen 40 ml. of a 2N hydrochloric acid solution is added thereto.Crystalline substances thus separated are recovered by filtration andwashed with water to give 4.38 g. of crude crystals. This product isrecrystallized from methanol to give 3.62 g. of the desired product aspale yellow columns having a melting point of 234°-235° C. Yield 69.3%

Analysis for C₁₂ H₁₁ N₃ C₄ (%): Calculated: C, 55.17; H, 4.24; N, 16.09.Found: C, 55.17; H, 4.14; N, 16.06.

EXAMPLE 2 1,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole

In 65 ml. of isopropanol are suspended 4.48 g. of1,3-dimethyl-5-pyrazolone and 3 g. of calcium hydroxide and theresulting suspension is heated under reflux for 30 minutes withstirring. After cooling, 8.4 g. of 2,4-dichlorobenzoyl chloride is addeddropwise thereto. After completion of the dropwise addition, the mixtureis heated under reflux for 2 hours. The solvent is distilled off fromthe reaction mixture and 15 ml. of water is added to the residue. Themixture is made acidic with 23 ml. of a 2N hydrochloric acid solutionand extracted with 60 ml. of chloroform. The chloroform layer is washedwith water and the organic phase is separated and dried. The chloroformis distilled off. The residue is recrystallized from ethanol to give 7.6g. of the desired product as colorless prisms of mp. 165°-166° C. Yield66.7%

Analysis for C₁₂ H₁₁ N₃ O₄ (%): Calculated: C, 50.55; H, 3.53; N, 9.82;Cl, 24.88. Found: C, 50.85; H, 3.54; N, 9.81; Cl, 24.55.

EXAMPLE 3 1-Methyl-3-n-propyl-4-(2-chlorobenzoyl)-5-hydroxypyrazole

1.4 g. of 1-methyl-3-n-propyl-5-pyrazolone is dissolved in 10 ml. ofdioxane with heating and then 1.5 g. of calcium hydroxide is added tothe resulting solution. 1.75 g. of 2-chlorobenzoyl chloride is addeddropwise with stirring at 50° C. After completion of the dropwiseaddition, the mixture is heated under reflux for 1 hour. Aftercompletion of the reaction, the reaction mixture is allowed to cool and100 ml. of a 2N hydrochloric acid solution is added thereto. The mixtureis extracted with 70 ml. of chloroform and an organic layer isseparated. The layer is washed with water, dried over anhydrous sodiumsulfate and the solvent is distilled off from the layer to give 2 g. ofbrown oily residue. The residue thus obtained is dissolved in a smallamount of benzene and adsorbed on a silica gel column, which is theneluted with benzene: ethanol (50:1) to give 0.6 g. of crystals. Thecrystals are recrystallized from methanol-water (7:3) to give 0.25 g. ofthe desired product as colorless columns having a melting point of125°-126° C. Yield 9.2%

Analysis for C₁₄ H₁₅ Cl N₂ O₂ (%) Calculated: C, 60.33; H, 5.42; N,10.05; Cl, 12.72. Found: C, 60.44; H, 5.43; N, 10.25; Cl, 12.72.

According to the procedures as in the above Examples 1 to 3, thefollowing compounds are prepared.

1,3-dimethyl-4-(3-chlorobenzoyl)-5-hydroxypyrazole m.p. 176.5°-177.5° C.

1,3-dimethyl-4-(4-chlorobenzoyl)-5-hydroxypyrazole m.p. 202°-204° C.

1,3-dimethyl-4-(2-chlorobenzoyl)-5-hydroxypyrazole m.p. 154°-155° C.

1,3-dimethyl-4-(3,4-dichlorobenzoyl)-5-hydroxypyrazole m.p. 255°-257° C.

1,3-dimethyl-4-(4-methylbenzoyl)-5-hydroxypyrazole m.p. 114°-116° C.

1,3-dimethyl-4-(3-methylbenzoyl)-5-hydroxypyrazole m.p. 145°-146° C.

1,3-dimethyl-4-(2-methoxybenzoyl)-5-hydroxypyrazole m.p. 162.5°-163.5°C.

1,3-dimethyl-4-(3-nitrobenzoyl)-5-hydroxypyrazole m.p. 246°-247° C.

1,3-dimethyl-4-(3,5-dinitrobenzoyl)-5-hydroxypyrazole m.p. 261°-262° C.

1,3-dimethyl-4-(4-bromobenzoyl)-5-hydroxypyrazole m.p. 207°-208° C.

1,3-dimethyl-4-(3,5-dichlorobenzoyl)-5-hydroxypyrazole m.p. 248°-249° C.

1,3-dimethyl-4-(2-nitrobenzoyl)-5-hydroxypyrazole m.p. 233°-234° C.

1,3-dimethyl-4-(4-benzoylbenzoyl)-5-hydroxypyrazole m.p. 194°-195° C.

1,3-dimethyl-4-(2-fluorobenzoyl)-5-hydroxypyrazole m.p. 158°-159° C.

1,3-dimethyl-4-(2-bromobenzoyl)-5-hydroxypyrazole m.p. 154°-156° C.

1,3-dimethyl-4-(2,5-dichlorobenzoyl)-5-hydroxypyrazole m.p. 183°-184° C.

1,3-dimethyl-4-(4-methoxybenzoyl)-5-hydroxypyrazole m.p. 214°-216° C.

1,3-dimethyl-4-(3,4-dimethoxybenzoyl)-5-hydroxypyrazole m.p. 154°-155°C.

1,3-dimethyl-4-(4-tert.-butylbenzoyl)-5-hydroxypyrazole m.p. 172°-173°C.

1,3-dimethyl-4-(3,4-dimethylbenzoyl)-5-hydroxypyrazole m.p. 197°-198° C.

1,3-dimethyl-4-(3,5-dimethylbenzoyl)-5-hydroxypyrazole m.p. 165°-167° C.

1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-5-hydroxypyrazole m.p.197°-197.5° C.

1-methyl-4-(2-chlorobenzoyl)-5-hydroxypyrazole m.p. 107°-110° C.

1,3-dimethyl-4-(3,5-dimethoxybenzoyl)-5-hydroxypyrazole m.p. 181°-182°C.

1,3-dimethyl-4-(2-nitro-5-methylbenzoyl)-5-hydroxypyrazole m.p.257°-258° C.

1,3-dimethyl-4-(4-methanesulfonylbenzoyl)-5-hydroxypyrazole m.p.257°-259° C.

1-isopropyl-3-methyl-4-(2-chlorobenzoyl)-5-hydroxypyrazole n_(D) ¹⁶1.5705

1,3-dimethyl-4-(2-iodobenzoyl)-5-hydroxypyrazole m.p. 171°-172° C.

1,3-dimethyl-4-(4-fluorobenzoyl)-5-hydroxypyrazole m.p. 181° C.

1,3-dimethyl-4-(4-cyanobenzoyl)-5-hydroxypyrazole m.p. 208° C.

1,3-dimethyl-4-(2-acetylbenzoyl)-5-hydroxypyrazole m.p. 142°-143° C.

1,3-dimethyl-4-(2,4,5-trichlorobenzoyl)-5-hydroxypyrazole m.p. 156°-157°C.

1,3-dimethyl-4-(2,3,4,5-tetrachlorobenzoyl)-5-hydroxypyrazole m.p.225°-226° C.

1,3-dimethyl-4-(3-methyl-4-nitrobenzoyl)-5-hydroxypyrazole m.p.252°-254° C.

1,3-dimethyl-4-(2-nitro-4-chlorobenzoyl)-5-hydroxypyrazole m.p.223°-224° C.

1,3-dimethyl-4-(3,4,5-trimethoxybenzoyl)-5-hydroxypyrazole m.p.189°-191° C.

1-ethyl-3-methyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole m.p.176°-177° C.

1-ethyl-3-methyl-4-(2-nitro-4-chlorobenzoyl)-5-hydroxypyrazole m.p.196°-197° C.

EXAMPLE 4 1,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-mercaptopyrazole

1.0 g. of 5-chloro-1,3-dimethylpyrazole, 1.05 g. of anhydrous aluminumchloride and 1.66 g. of 2,4-dichlorobenzoyl chloride are dissolved in 6ml. of tetrachloroethane and the resulting solution is heated underreflux for 8 hours. After completion of the reaction, the reactionmixture is poured into water and an organic layer is separated. 7 ml. ofa 5% aqueous solution of sodium hydroxide is added thereto and themixture is stirred for 1 hour. Then, the organic layer is dried overanhydrous sodium sulfate and the solvent is distilled off from thelayer. The resulting oily substance is crystallized from ethanol to give1.82 g. of 5-chloro-4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazole asprisms melting at 101.5°-102.5° C. Yield 78.3%

Analysis for C₁₂ H₉ Cl₃ N₂ O (%): Calculated: C, 47.48; H, 2.99; N,9.23; Cl, 35.04. Found: C, 47.49; H, 2.96; N, 9.31; Cl, 34.91.

A mixture of 0.3 g. of5-chloro-4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazole, 2.1 g. of sodiumhydrogen sulfide 2 hydrate and 6 ml. of ethanol is heated under refluxon a water bath for 3 hours. After completion of the reaction, theethanol is distilled off under reduced pressure from the reactionmixture and 15 ml. of water is added followed by extraction withbenzene. To an aqueous layer is added conc. hydrochloric acid to adjustthe pH to 1 and the mixture is extracted with chloroform. The extract iswashed with water and then dried over anhydrous sodium sulfate. Thesolvent is distilled off from the extract to give the crude crystallinesubstance, which is then recrystallized from n-hexane to give 0.10 g. ofthe desired product as yellow powders having a melting point of 85°-86°C. Yield 33.3%.

Analysis for C₁₂ H₁₀ N₂ OSCl₂ (%): Calculated: C, 47.85; H, 3.35; N,9.30; S, 10.65; Cl, 23.54. Found: C, 47.76; H, 3.43; N, 9.38; S, 11.02;Cl, 23.24.

EXAMPLE 5 1,3-Dimethyl-4-(2,6-dichlorobenzoyl)-5-hydroxypyrazole

In 5 ml. of water is dissolved 0.56 g. of potassium hydroxide and asolution of 1.52 g. of5-chloro-4-(2,6-dichlorobenzoyl)-1,3-dimethylpyrazole in 10 ml. ofethanol is added thereto. The mixture is heated under reflux for 12hours. After completion of the reaction, the reaction mixture is allowedto cool and extracted with benzene. An aqueous layer is separated and 2NHCl solution is added to adjust the pH to 3-4, whereby crystallinesubstance is separated out. The resulting crystalline substance isrecovered by filtration and recrystallized from ethanol to give 0.68 g.of the desired product as colorless needles melting at 249.5°-250.5° C.Yield 48.0%.

Analysis for C₁₂ H₁₀ Cl₂ N₂ O₂ (%): Calculated: C, 50.55; H, 3.53; N,9.82; Cl, 24.88. Found: C, 50.38; H, 3.53; N, 9.90; Cl, 24.57.

In accordance with the procedures of the above-mentioned Example 5 areprepared the following compounds.

1,3-dimethyl-4-(2,4-dimethylbenzoyl)-5-hydroxypyrazole m.p. 95°-96° C.

1,3-dimethyl-4-(2-methylbenzoyl)-5-hydroxypyrazole m.p. 82°-83° C.

EXAMPLE 6 1,3-Dimethyl-4-(2-chlorobenzoyl)-5-acetoxypyrazole

In a mixture of 20 ml. of benzene and 0.51 g. of triethylamine isdissolved 1.25 g. of 1,3-dimethyl-4-(2-chlorobenzoyl)-5-hydroxypyrazoleand 0.4 g. of acetyl chloride is added dropwise at room temperature withstirring. After completion of the dripwise addition, the mixture isstirred at room temperature for 3 hours. After completion of thereaction, water is added to the reaction mixture to dissolve the saltsand an organic layer is separated. The organic layer is dried overanhydrous sodium sulfate and the solvent os distilled off. The resultingoily substance is recrystallized from n-hexane to give crude crystallinesubstance. The substance is recrystallized from methanol to give 1.20 g.of the desired product as colorless prisms melting at 78°-79° C. Yield82.2%.

Analysis for C₁₄ H₁₃ Cl N₂ O₃ (%): Calculated: C, 57.45; H, 4.48; N,9.57; Cl, 12.11. Found: C, 57.50; H, 4.45; N, 9.61; Cl, 12.23.

IR spectrum Nujol ν_(c)═o 1793cm⁻¹

EXAMPLE 7 1,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-lauroyloxypyrazole

In 10 ml. of benzene is dissolved 0.285 g. of1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole and then 0.2 ml.of triethylamine is added thereto. Under ice-cooling, a solution of 0.27g. of lauroyl chloride in 5 ml. of benzene is added dropwise thereto.After completion of the dropwise addition, the resulting mixture isstirred at room temperature for 19 hours. After completion of thereaction, ether is added to the reaction mixture, which is then washedsuccessively with water, 1N HCl, a saturated aqueous solution of sodiumhydrogencarbonate and a saturated aqueous solution of sodium chloride.Then, the reaction mixture is dried over anhydrous sodium sulfate andthe solvent is distilled off from the reaction mixture. The resultingresidue is recrystallized from n-hexane under cooling with dry-ice togive 0.46 g. of the desired product as white crystals melting at 56° C.Yield 98.0%.

Analysis for C₂₄ H₃₂ Cl₂ N₂ O₃ (%): Calculated: C, 61.66; H, 6.90; N,5.99; Cl, 15.17. Found: C, 61.27; H, 6.94; N, 5.84; Cl, 15.11.

IR spectrum Nujol ν_(c)═o 1790cm⁻¹

EXAMPLE 8 1,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-chloroacetoxypyrazole

In a mixture of 10 ml. of benzene and 0.2 ml. of triethylamine isdissolved 0.285 g. of1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole and then asolution of 0.18 g. of chloroacetylchloride in 5 ml. of benzene is addeddropwise under ice-cooling and stirring. After completion of thedropwise addition, the resulting mixture is stirred at room temperaturefor 2 hours. After completion of the reaction, ether is added to thereaction mixture and the mixture is then washed successively with 3portions of 50 ml. of water and dried over anhydrous sodium sulfate.Then, the solvent is distilled off from the mixture and the resultingresidue is recrystallized from n-hexane to give 0.297 g. of the desiredproduct as white crystals melting at 120°-122° C. Yield 82.0%.

Analysis for C₁₄ H₁₁ Cl₃ N₂ O₃ (%): Calculated: C, 46.50; H, 3.07; N,7.25; Cl, 29.41. Found: C, 46.25; H, 3.08; N, 7.81; Cl, 29.32.

IR spectrum Nujol ν_(c)═o 1790cm⁻¹

In accordance with the procedures of the above-mentioned Examples 6-8are prepared the following compounds.

1,3-dimethyl-4-(2-chlorobenzoyl)-5-(N,N-dimethylcarbamoyloxy)pyrazolem.p. 115°-116° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-stearoyloxypyrazole m.p. 57°-61°C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-crotonyloxypyrazole m.p. 87°-89°C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-benzoyloxypyrazole m.p. 138°-139°C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-acetoxypyrazole m.p. 81°-82° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-acetylthiopyrazole n_(D) ¹⁷.51.5890

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-propionyloxypyrazole m.p. 48° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-isobutyryloxypyrazole m.p.101°-102° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-linoleyloxypyrazole n_(D) ¹³.81.5196

1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-5-benzoyloxypyrazole m.p. 163°C.

1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-5-(4-chlorobenzoyloxy)pyrazolem.p. 194° C.

1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-5-(2-chloro-4-nitrobenzoyloxy)pyrazolem.p. 182°-184° C.

1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-5-cinnamoyloxypyrazole m.p.164° C.

bis[1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-5-pyrazolyl]succinate m.p.203° C.

1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-5-acetoxypyrazole m.p. 133° C.

1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-5-pivaloyloxypyrazole m.p.157°-158° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-phenylacetoxypyrazole m.p.74°-76° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-(4-chlorophenylacetoxy)pyrazolem.p. 130°-131° C.

1,3-dimethyl-4-(4-nitrobenzoyl)-5-acetoxypyrazole m.p. 179°-180° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-cyclohexylcarbonyloxypyrazolem.p. 98°-99° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-(2,4-dichlorophenoxyacetoxy)pyrazolem.p. 107°-108° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-(2,4-dichlorobenzoyloxy)pyrazolem.p. 168°-169° C.

bis[1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-pyrazolyl]sebacate m.p.143°-144° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-(4-methylbenzoyloxy)pyrazole m.p.197°-198° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-pivaloyloxypyrazole m.p. 94° C.

EXAMPLE 91,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-pyrazolylmethanesulfonate

In a mixture of 0.1 g. of triethylamine and 5 ml. of dry benzene isdissolved 0.29 g. of1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole and then 0.1 g.of methanesulfonyl chloride is added dropwise at room temperature withstirring. After completion of the dropwise addition, the resultingmixture is stirred at room temperature for 12 hours. After completion ofthe reaction, 10 ml. of water is added to the reaction mixture. Then, anorganic layer is separated. The organic layer is dried over anhydroussodium sulfate and the solvent is distilled off. The resulting residueis recrystallized from n-hexane to give 0.3 g. of the desired product aswhite needles melting at 73°-74° C. Yield 83.3%.

Analysis for C₁₃ H₁₂ Cl₂ N₂ O₄ S (%): Calculated: C, 42.99; H. 3.33; N,7.71; S, 8.83; Cl, 19.25. Found: C, 42.64; H, 3.37; N, 7.76; S, 9.15;Cl, 19.23.

IR spectrum Nujol ν_(SO).sbsb.2 1355cm⁻¹ 1180cm⁻¹

In accordance with the procedure of the above-mentioned Example 9 areprepared the following compounds.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-pyrazolyl 4-toluenesulfonate m.p.122°-124° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-pyrazolyl benzenesulfonate m.p.88°-89° C.

1,3-dimethyl-4-(2-nitro-4-chlorobenzoyl)-5-pyrazolyl 4-toluenesulfonatem.p. 129°-130° C.

1,3-dimethyl-4-(2-nitro-4-chlorobenzoyl)-5-pyrazolyl benzenesulfonatem.p. 127°-128° C.

1-ethyl-3-methyl-4-(2,4-dichlorobenzoyl)-5-pyrazolyl 4-toluenesulfonatem.p. 115°-116° C.

1-ethyl-3-methyl-4-(2-nitro-4-chlorobenzoyl)-5-pyrazolyl4-toluenesulfonate m.p. 100°-101° C.

1,3-dimethyl-4-(2-chlorobenzoyl)-5-pyrazolyl methanesulfonate m.p.97°-98° C.

EXAMPLE 101,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-(5-methyl-3-oxo-4-isoxazolin-2-ylcarbonyloxy)pyrazole

In 4 ml. of dry benzene is dissolved 0.1 g. of3-hydroxy-5-methylisoxazole and then 0.5 g. of liquid phosgene is addedthereto. After stirring at room temperature for 1 hour, the mixture isheated under reflux for 1 hour. After completion of the reaction, thereaction mixture is allowed to cool and the excess phosgene and benzeneare distilled off under reduced pressure. The residue is dissolved in 5ml. of dry benzene and a solution of 0.3 g. of4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-hydroxypyrazole and 0.1 g. oftriethylamine in 5 ml. of dry benzene is added dropwise at roomtemperature with stirring. After completion of the dropwise addition,the mixture is stirred at room temperature for further 1 hour. Aftercompletion of the reaction, 10 ml. of water is added to the reactionmixture and then an organic layer is separated. The organic layer iswashed successively with 1N HCl, a saturated aqueous solution of sodiumhydrogen carbonate and water and dried over anhydrous sodium sulfate.Then, the solvent is distilled off and the resulting residue isrecrystalized from benzene-hexane to give 0.25 g. of the desired productas white needles melting at 180°-182° C. Yield 61.0%.

Analysis for C₁₇ H₁₃ Cl₂ N₃ O₅ (%): Calculated: C, 49.78; H, 3.19; N,10.24; Cl, 17.28. Found: C, 49.75; H, 3.31; N, 10.31; Cl, 17.05.

IR spectrum Nujol ν_(c)═o 1785cm⁻¹

In accordance with the procedures of the above-mentioned Example 10 isprepared the following compound.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-(3-oxo-4-chloro-5-methyl-4-isoxazolin-2-ylcarbonyloxy)pyrazolem.p. 204°-206° C.

EXAMPLE 111,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-methoxycarbonyloxypyrazole

In a mixture of 20 ml. of dry benzene and 0.28 g. of triethylamine isdissolved 0.72 g. of1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole and then 0.26 g.of methyl chlorocarbonate is added dropwise at room temperature withstirring. After completion of the dropwise addition, the mixture isstirred at room temperature for 1 hour. After completion of thereaction, the reaction mixture is allowed to stand for 12 hours and then30 ml. of water is added thereto. Then, a benzene layer is separated andan aqueous layer is extracted with benzene. The benzene layer and thebenzene extract are combined and the mixture is washed with water anddried over anhydrous sodium sulfate. Then, the solvent is distilled offfrom the benzene solution and the resulting residue is recrystallizedfrom a small amount of n-hexane to give 0.77 g. of the desired productas white crystals melting at 86°-88° C. Yield 92%.

Analysis for C₁₄ H₁₂ Cl₂ N₂ O₄ (%): Calculated: C, 49.00; H, 3.52; N,8.16; Cl, 20.66. Found: C, 49.05; H, 3.56; N, 8.33; Cl, 20.44.

IR spectrum Nujol ν_(c)═o 1771cm⁻¹

In accordance with the procedures of the above-mentioned Example 11 areprepared the following compounds.

1,3-dimethyl-4-(2-chlorobenzoyl)-5-methoxycarbonyloxypyrazole m.p.69°-70° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-n-propoxycarbonyloxypyrazole m.p.59°-62° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-benzyloxycarbonyloxypyrazole m.p87°-90° C.

bis[1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-pyrazolyl]carbonate m.p.166°-168° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-phenoxycarbonyloxypyrazole m.p.159°-160° C.

1,3-dimethyl-4-(b 2,4-dichlorobenzoyl)-5-phenylthiocarbonyloxypyrazolem.p. 83°-84° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-n-butylthiocarbonyloxypyrazolen_(D) ¹⁶ 1.5618

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-ethylthiocarbonyloxypyrazolen_(D) ²³ 1.5751

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-benzylthiocarbonyloxypyrazolen_(D) ²³ 1.5904

EXAMPLE 12 O,O-DiethylO-[1,3-dimethyl-4-(2-chlorobenzoyl)-5-pyrazolyl]phosphorothioate

A mixture of 1.0 g. of4-(2-chlorobenzoyl)-1,3-dimethyl-5-hydroxypyrazole, 20 ml. of benzene,0.433 g. of triethylamine and 0.81 g. of O,O-diethylthiophosphoricchloride is heated under reflux with stirring for 6.5 hours. Aftercompletion of the reaction, the reaction mixture is allowed to cool andwater is added to dissolve salts. An organic layer is separated, washedwith water, dried over anhydrous sodium sulfate and the solvent isdistilled off. The resulting oily substance is column-chromatographedover 10 g. of silica gel and then recrystallized from n-hexane to give0.28 g. of the desired product melting at 71°-74° C. Yield 17.8%.

Analysis for C₁₆ H₂₀ Cl N₂ O₄ PS (%): Calculated: C, 47.41; H, 5.00; N,6.95; Cl, 8.80; P, 7.69. Found: C, 47.83; H, 4.94; N, 6.76; Cl, 9.08; P,7.35.

EXAMPLE 13 1,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazolecalcium salt

In 50 ml. of water is suspended 2.85 g. of1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole and thesuspension is dissolved in about 5 ml. of a 2N aqueous solution ofsodium hydroxide. A solution of 1.11 g. of calcium chloride in 10 ml. ofwater is added and the resulting mixture is stirred. The so separatedprecipitates are recovered by filtration and dried to give 2.4 g. of thedesired product as white powder melting at about 260° C. Yield 79.0%.

Analysis for C₁₂ H₉ N₂ O₂ Cl₂ Ca/2.H₂ O (%): Calculated: C, 44.73; H,3.44; N, 8.69. Found: C, 47.88; H, 3.23; N, 8.83.

In accordance with the procedure of the above-mentioned Example 13 areprepared the following compounds.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole magnesium saltm.p. ca. 270° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole aluminum saltm.p. ca. 155° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole iron salt m.p.ca. 170° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole copper salt m.p.above 300° C.

1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole sodium salt m.p.above 300° C.

EXAMPLE 14 1,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazoleisopropylamine salt

In 50 ml. of benzene is suspended 2.85 g. of1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole and 0.7 g. ofisopropylamine is added to the suspension with stirring. Then, theresulting mixture is stirred at room temperature for about 1 hour. Thesolvent is distilled off from the reaction mixture. The residue iscooled. The so separated solid material is recovered by filtration,washed with petroleum ether and dried to give 3.2 g. of the desiredproduct as white powdery substance melting at 130°-140° C. Yield 93.2%.

Analysis for C₁₅ H₁₉ Cl₂ N₃ O₂ (%): Calculated: C, 52.34; H, 5.56; N,12.21. Found: C, 52.09; H, 5.72; N, 12.59.

EXAMPLE 15 1,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazolehydrochloride

To 0.3 g. of 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole isadded 2 ml. of conc. HCl and the resulting mixture is stirred at roomtemperature for 6 hours. After completion of the reaction, the reactionmixture is allowed to cool and the so separated desired product isrecovered by filtration. The product is washed with a small amount ofmethanol and then with n-hexane and next dried to give 0.20 g. of thedesired product as white powders having a melting point of 115°-125° C.(with decomp.) Yield 57.1%.

Analysis for C₁₂ H₁₁ N₂ Cl₃ O₂ (%): Calculated: C, 44.82; H, 3.45; N,8.71; Cl, 33.07. Found: C, 45.16; H, 3.57; N, 8.85; Cl, 32.93.

In accordance with the procedures of the above-mentioned Example 15 isprepared the following compound.

1,3-dimethyl-4-(3,4-dimethoxybenzoyl)-5-hydroxypyrazole hydrochloridem.p. 164°-165° C.

EXAMPLE 16 1-Allyl-3-methyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole

A suspension of 1.4 g. of 1-allyl-3-methyl-2-pyrazolin-5-one and 0.74 g.of calcium hydroxide in 20 ml. of isopropanol is heated under refluxwith stirring for 1.5 hours. After cooling, to the resulting mixture isadded dropwise 2.3 g. of 2,4-dichlorobenzoyl chloride. After completionof the dropwise addition, the resulting mixture is heated under refluxfor 5.5 hours. After completion of the reaction, the solvent isdistilled off from the reaction mixture and to the residue is added 3ml. of 2N hydrochloric acid to adjust pH to 3.0. Then, the mixture isextracted with chloroform and the extract solvent is distilled off fromthe extract. The residue is dissolved in a small amount of benzene andthe solution is washed with water, dried over anhydrous sodium sulfateand the solvent is distilled off. The resulting residue isrecrystallized from isopropyl ether containing a small amount ofmethylene chloride to give 1.18 g. of the desired product as whitecrystals melting at 161°-163° C. Yield 40.7%.

Analysis for C₁₂ H₁₆ N₂ Cl₂ O₃ (%): Calculated: C, 47.86; H, 3.35; N,9.30; Cl, 23.54. Found: C, 47.33; H, 3.41; N, 9.06; Cl, 23.31.

EXAMPLE 17 1-Allyl-3-methyl-4-(2,4-dichlorobenzoyl)-5-pyrazolyl4-toluenesulfonate

To a solution of 180 mg. of1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole in 6 ml. ofbenzene and 58.4 mg. of triethylamine is added dropwise 110 mg. of4-toluenesulfonyl chloride with stirring at room temperature. Then, theresulting mixture is heated under reflux for 1 hour. After completion ofthe reaction, water is added to the reaction mixture and an organiclayer is separated. The organic layer is dried over anhydrous sodiumsulfate, the solvent is distilled off and the resulting oily substanceis recrystallized from benzene-n-hexane to give 173 mg. of the desiredproduct as colorless prisms melting at 113°-114° C. Further, the solventis distilled off from the mother liquor and recrystallization fromn-hexane gives 26 mg. of the desired product. Total yield 73.9%

Analysis for C₂₁ H₁₈ O₄ N₂ S Cl₂ (%): Calculated: C, 54.20; H, 3.90; N,6.02; S, 6.89; Cl, 15.24. Found: C, 54.45; H, 3.98; N, 6.07; S, 6.80;Cl, 15.19.

According to the same procedures as in Example 17 are prepared thefollowing compounds:

1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-5-(4-chlorobenzoyloxy)pyrazolem.p. 155°-157° C.

1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-5-isobutyryloxypyrazole m.p.62°-63° C.

1-allyl-3-methyl-4-(2-chloro-4-nitrobenzoyl)-5-pyrazolyl4-toluenesulfonate m.p. 96°-99° C.

examples of the preparations of the present herbicidal composition aregiven below. All parts are given by weight hereinafter unless otherwisestated.

EXAMPLE 18 Granules

70 parts of the compound designated as Compound No. 11 are finelypulverized and 30 parts of clay are added thereto. The mixture isblended in a mixer to form a premix. 10 parts of the premix arehomogeneously blended with 60 parts of clay and 30 parts of bentonite ina mixer. To the resulting blend is added an appropriate amount of water.The mixture is kneaded in a kneader, extruded through a screen having adiameter of 0.8 mm. and dried in a draft drier at 50° C. The so obtainedproduct is adjusted by a shifter to give granules.

EXAMPLE 19 Granules

70 parts of the compound designated as Compound No. 183 are finelypulverized and 30 parts of clay are added thereto. The mixture isblended in a mixer to form a premix. 10 parts of the premix arehomogeneously blended with 60 parts of clay and 30 parts of bentonite ina mixer. To the resulting blend is added an appropriate amount of water.The mixture is kneaded in a kneader, extruded through a screen having adiameter of 0.8 mm. and dried in a draft drier at 50° C. The so obtainedproduct is adjusted by a shifter to give granules.

EXAMPLE 20 Granules

35 parts of the compound designated as Compound No. 11 and 35 parts ofS-(4-chlorobenzyl)N,N-diethylthiolcarbamate are finely pulverized and 30parts of white carbon are added thereto. The mixture is blended in amixer to form a premix. 20 parts of the premix are homogeneously blendedwith 50 parts of clay and 30 parts of bentonite in a mixer. To theresulting blend is added an appropriate amount of water. The mixture iskneaded in a kneader, extruded through a screen having a diameter of 0.8mm. and dried in a draft drier at 50° C. The so obtained product isadjusted by a shifter to give granules.

EXAMPLE 21 Wettable powders

50 parts of the compound designated as Compound No. 32, 29 parts ofclay, 10 parts of diatomaceous earth, 5 parts of white carbon, 3 partsof sodium ligninsulfonate, 2 parts of "Newcoal" 1106 (trade name, NihonNyukazai K. K., Japan) and 1 part of polyvinyl alcohol are homogeneouslyblended in a mixer and pulverized three times by means of a hammer millto give wettable powders.

EXAMPLE 22 Emulsifiable concentrates

20 parts of the compound designated as Compound No. 18, 65 parts ofxylene and 15 parts of "Paracoal" PS (trade name, Nihon Nyukazai K. K.,Japan) are blended and homogeneously dissolved to form emulsifiableconcentrates.

EXAMPLE 23 Solutions

30 parts of the compound designated as Compound No. 69, 1 part of"Newcoal" 565 (trade name, Nihon Nyukazai K. K., Japan) and 69 parts ofwater are blended and homogeneously dissolved to form solutions.

Experimental examples of the present herbicidal compositions thusprepared are given below. The wettable powders prepared according to theprocedures in the above-mentioned Example 21 are used in the followingexperiments, each containing 50% by weight of the active compound ofthis invention.

EXPERIMENT 1. Water Surface Application Tests For Paddy Field WeedControl

3 polyethylene pots (hereinafter abbreviated as A,B and C), each havingthe surface of 45 cm², were packed with paddy field soil. In Pot A weretransplanted rice seedlings (two plants) (variety: Kinmaze at 2.5 leafstage) and two tubers of "Urikawa" as a representative of perennialweed. In Pot B, seeds of monochoria, false pimpernel and "Abunome"(Dopatrium junceum Hamilt) as representatives of broad-leaf weed wereincorporated in the soil, a block of runners of slender spikerush wastransplanted thereinto and two tubers of "Mizugayatsuri" as perenialweed were planted in the soil. In Pot C, seeds of barnyardgrass and"Hotarui" (Scirpus hotarui Ohwi) as representatives of narrow-leaf weedwere incorporated in the soil and two tubers of "Omodaka" as perennialweed were planted in the soil. The Pots A, B and C were kept in a greenhouse for 3 days under a paddy field condition. After rooting of plants,suspensions of test chemicals were applied into the paddy water at 10ml. per Pot. After 20 days from the treatment, herbicidal effects oneach weed and phytotoxicity to rice plants were observed and evaluated.The results are shown in Table 1 wherein effective does (g/a) means theminimum dose for growth inhibition rate to each test plant (percentageleaf area suffered chlorosis) of not less than 70%.

                                      Table 1                                     __________________________________________________________________________    Herbicidal Activity in Paddy Field                                            (Effective dose g/a)                                                                                                           Rice                                     Broad-                               seedling                     Compound                                                                            Barnyard-                                                                           weed              Slender                                                                             "Mizugaya-   trans-                       No.   grass leaf  "Hotarui"                                                                           "Urikawa"                                                                           spikerush                                                                           tsuri"                                                                              "Omodake"                                                                            planted                      __________________________________________________________________________    1     100   25    75    100   75    100   50     >800                         2     50    25    75    100   25    50    25     >800                         3     25    6.25  12.5  50    12.5  12.5  25     400                          4     75    25    50    75    200   50    50     400                          5     75    50    75    200   100   75    50     >800                         6     75    50    50    75    25    75    50     400                          8     75    50    50    50    50    25    25     400                          9     25    12.5  12.5  100   6.25  6.25  100    200                          10    75    75    75    200   25    50    200    >800                         11    6.25  6.25  12.5  6.25  50    12.5  12.5   200                          13    25    75    75    50    100   75    100    200                          14    6.25  6.25  6.25  6.25  25    6.25  12.5   100                          15    400   6.25  100   75    75    75    100    >800                         16    12.5  6.25  12.5  12.5  25    6.25  25     400                          18    12.5  6.25  25    12.5  12.5  12.5  50     400                          19    12.5  6.25  6.25  12.5  12.5  12.5  12.5   100                          21    25    25    25    12.5  25    25    50     400                          22    12.5  12.5  6.25  12.5  12.5  12.5  12.5   400                          23    50    12.5  25    6.25  12.5  12.5  12.5   >800                         24    50    50    50    50    75    75    50     400                          26    12.5  12.5  6.25  12.5  12.5  25    12.5   100                          28    200   50    100   25    75    400   75     400                          29    50    6.25  50    12.5  75    25    50     400                          30    50    100   75    50    400   75    200    >800                         32    6.25  6.25  6.25  12.5  12.5  25    50     200                          33    12.5  12.5  12.5  75    100   25    75     400                          35    25    12.5  25    12.5  50    25    25     >800                         36    12.5  6.25  25    25    75    200   50     >800                         38    25    6.25  12.5  12.5  12.5  12.5  12.5   200                          39    6.25  6.25  6.25  6.25  50    25    25     100                          40    50    50    75    6.25  75    75    50     >800                         41    6.25  12.5  6.25  12.5  25    12.5  25     400                          42    25    12.5  50    100   100   400   100    >800                         43    6.25  25    50    50    100   75    100    200                          44    6.25  12.5  12.5  25    25    25    25     400                          45    25    6.25  12.5  12.5  12.5  12.5  12.5   200                          46    25    6.25  12.5  12.5  12.5  12.5  12.5   400                          47    6.25  6.25  6.25  6.25  12.5  6.25  12.5   >800                         48    6.25  6.25  6.25  12.5  6.25  6.25  12.5   200                          49    6.25  6.25  6.25  12.5  25    12.5  12.5   200                          51    12.5  6.25  12.5  12.5  12.5  6.25  50     400                          52    50    6.25  50    75    75    25    75     >800                         53    100   6.25  50    6.25  50    50    50     >800                         54    200   6.25  200   12.5  75    75    100    >800                         56    6.25  6.25  6.25  12.5  12.5  12.5  6.25   400                          57    6.25  6.25  12.5  6.25  6.25  6.25  12.5   200                          58    6.25  6.25  6.25  12.5  12.5  12.5  12.5   200                          59    6.25  6.25  25    12.5  6.25  6.25  12.5   400                          60    6.25  6.25  12.5  25    12.5  12.5  12.5   400                          61    6.25  6.25  12.5  6.25  25    6.25  12.5   200                          63    6.25  6.25  12.5  12.5  6.25  12.5  6.25   100                          64    12.5  6.25  12.5  6.25  6.25  6.25  25     200                          65    12.5  6.25  12.5  12.5  12.5  6.25  12.5   200                          66    12.5  6.25  6.25  12.5  6.25  12.5  25     200                          67    6.25  6.25  6.25  2.5   6.25  6.25  12.5   200                          68    12.5  6.25  12.5  12.5  25    6.25  12.5   200                          69    6.25  6.25  12.5  12.5  12.5  6.25  12.5   200                          71    12.5  6.25  12.5  25    25    25    75     100                          72    12.5  12.5  25    25    100   12.5  25     400                          73    12.5  6.25  12.5  12.5  50    12.5  25     400                          74    12.5  6.25  12.5  25    25    12.5  25     200                          76    6.25  6.25  12.5  6.25  25    6.25  25     400                          77    6.25  6.25  6.25  6.25  12.5  12.5  12.5   200                          78    12.5  6.25  25    25    50    50    50     400                          79    6.25  6.25  12.5  12.5  25    12.5  100    400                          80    6.25  6.25  6.25  12.5  25    6.25  25     400                          81    6.25  6.25  25    6.25  50    6.25  25     200                          82    6.25  6.25  6.25  12.5  25    200   12.5   200                          83    6.25  6.25  6.25  12.5  50    6.25  12.5   200                          84    12.5  12.5  25    12.5  25    25    12.5   200                          85    6.25  6.25  12.5  12.5  25    6.25  25     200                          86    12.5  12.5  25    6.25  25    6.25  25     400                          87    12.5  12.5  6.25  12.5  12.5  6.25  50     >800                         88    25    12.5  25    25    25    25    25     400                          90    25    12.5  25    12.5  25    12.5  12.5   400                          91    12.5  6.25  12.5  12.5  25    12.5  12.5   400                          92    200   6.25  75    50    75    75    100    >800                         94    25    12.5  12.5  75    12.5  25    75     200                          95    6.25  6.25  12.5  12.5  25    6.25  25     200                          96    6.25  6.25  6.25  6.25  6.25  12.5  6.25   100                          97    12.5  6.25  25    12.5  25    12.5  12.5   200                          98    75    75    75    25    25    50    200    >800                         100   12.5  12.5  25    25    25    25    25     400                          101   12.5  25    6.25  12.5  50    25    25     200                          102   25    12.5  12.5  6.25  50    25    50     400                          103   12.5  6.25  12.5  6.25  25    50    50     400                          104   12.5  12.5  25    6.25  25    25    12.5   400                          105   6.25  12.5  25    25    25    12.5  25     100                          106   12.5  12.5  25    25    25    12.5  25     100                          107   25    50    25    6.25  50    50    50     400                          108   25    25    25    12.5  50    25    50     100                          109   25    50    50    12.5  50    50    50     400                          110   25    12.5  75    50    25    50    25     400                          111   12.5  25    25    12.5  50    50    25     400                          112   25    25    50    12.5  50    50    25     400                          115   12.5  12.5  25    12.5  50    25    12.5   400                          125   6.25  12.5  12.5  25    25    12.5  50     200                          135   12.5  25    50    12.5  50    25    25     400                          141   12.5  12.5  25    6.25  25    25    12.5   400                          163   25    12.5  25    6.25  12.5  50    25     400                          __________________________________________________________________________

EXPERIMENT 2 Pre-emergency Application Tests For Upland Weed Control

In a polyethylene pot having the surface of 150 cm² were filled soil andseeds of barnyard grass, crabgrass, green foxtail, goose grass and"Kayatsurigusa" as representatives of narrow-leaf weed and of shepherd'spurse as a representative of broad-leaf weed were sown and covered withsoil.

Another polyethylene pot having the surface of 150 cm² was filled withsoil and seeds of asati dayflower as narrow-leaf weed and commonchickweed, corn spurrey, pigweed, common pursland and commonlamb's-quaters as representatives of broad-leaf weed were sown andcovered with soil.

Immediately after soil-covering, suspensions of test compounds wereapplied to soil surface at the rate of 10 ml. per pot. After 20 daysfrom the application, herbicidal effects on each weed were observed. Theresults are shown in Table 2 wherein ratings for evaluation are the sameas in Experiment 1 and shown by means of effective dose (g/a).

                                      Table 2                                     __________________________________________________________________________    Herbicidal activity in field                                                  (Effective dose g/a)                                                                                      common                                                                             asatic             common                    Compound                                                                            barnyard                                                                           crab-                                                                             green                                                                             goose                                                                             "Kayat-                                                                            chick-                                                                             day-                                                                              corn      common                                                                             lamb's                                                                             shepherd's           No.   grass                                                                              grass                                                                             foxtail                                                                           grass                                                                             surigusa"                                                                          weed flower                                                                            spurrey                                                                            pigweed                                                                            purslane                                                                           quarters                                                                           purse                __________________________________________________________________________    3     50   50  50  50  25   25   400 25   200  100  50   50                   4     100  100 50  50  25   200  400 400  50   50   100  100                  9     50   25  50  25  25   100  100 400  50   200  100  100                  11    50   200 400 400 50   25   400 25   200  50   50   50                   14    25   50  25  25  25   25   100 25   50   50   25   25                   16    200  200 200 200 25   100  800 100  800  25   25   400                  19    50   25  25  25  25   25   100 25   50   25   25   25                   26    100  100 100 25  25   200  400 400  50   25   50   50                   32    25   25  50  25  25   400  100 25   25   25   25   25                   38    100  200 400 50  25   25   100 25   800  25   100  50                   39    25   25  50  25  25   25   100 25   25   25   100  25                   43    25   25  25  25  25   25   100 25   50   25   25   25                   44    100  50  50  50  25   25   200 50   100  25   25   50                   47    50   50  25  50  25   25   50  25   50   25   25   25                   49    50   100 100 50  25   25   200 25   100  25   25   25                   51    200  200 200 100 25   25   200 25   100  25   25   25                   56    100  400 100 100 25   25   200 25   25   25   25   25                   57    100  400 100 100 25   25   200 25   25   25   25   25                   58    100  200 100 200 25   25   50  25   25   25   50   25                   59    100  400 100 200 25   25   400 25   50   25   25   25                   60    100  400 100 100 25   25   200 25   100  200  25   25                   61    100  800 100 100 25   25   200 25   25   50   25   25                   63    100  200 100 100 25   25   100 25   25   25   25   25                   64    100  400 100 100 25   25   200 25   200  25   25   25                   65    100  800 200 400 25   25   25  200  50   25   25   25                   66    100  800 100 400 25   25   25  100  50   25   25   25                   67    200  800 50  100 25   25   25  25   25   25   25   25                   68    100  200 100 100 25   25   200 50   25   25   25   25                   69    100  400 100 100 25   25   200 25   50   25   25   25                   76    100  100 100 50  25   25   200 25   25   50   25   25                   78    100  100 200 200 25   100  800 200  400  200  100  200                  79    100  100 100 100 25   200  800 200  100  100  100  100                  80    25   50  50  50  25   25   200 50   25   25   50   25                   81    50   50  25  25  25   25   100 25   25   25   25   25                   83    200  100 200 200 25   25   400 25   50   25   25   25                   85    100  400 100 100 25   500  100 25   200  25   50   25                   86    100  400 100 100 50   25   100 25   50   25   25   25                   87    100  400 100 100 25   50   100 50   25   25   25   25                   88    200  100 400 50  25   50   100 25   400  25   100  50                   90    50   50  25  25  50   25   400 25   200  100  50   50                   94    50   25  50  50  25   100  100 400  50   100  50   50                   96    100  200 100 100 25   25   50  25   50   25   25   50                   100   200  200 100 100 50   25   400 25   100  25   50   50                   101   100  200 50  400 50   25   200 25   50   25   25   25                   103   200  400 400 400 200  25   400 50   100  50   25   50                   105   100  100 50  50  50   25   50  25   25   25   25   25                   106   50   100 50  50  25   25   100 25   25   25   25   25                   107   400  200 100 100 100  25   400 50   100  25   25   50                   108   50   50  50  100 25   25   200 25   25   25   25   25                   109   400  100 100 100 100  25   200 50   200  50   25   25                   110   50   200 100 100 50   50   200 25   100  100  50   50                   115   100  200 200 100 50   25   400 100  200  200  200  100                  125   50   50  50  50  50   25   200 25   100  100  50   25                   135   200  200 200 200 100  50   400 25   200  200  200  200                  141   100  100 100 100 50   25   400 100  100  200  100  100                  183   200  200 200 400 100  25   200 25   25   25   25   25                   __________________________________________________________________________

It will be apparent from the above results that the pyrazole compounds(I) in this invention have excellent herbicidal activities and thus theyare practically useful as a herbicide for paddy field, upland field,non-crop land and so on.

What is claimed is:
 1. 1,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-pyrazolylmethanesulfonate.
 2. 1,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-pyrazolyl4-toluenesulfonate.
 3. 1,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-pyrazolylbenzenesulfonate. 4.1,3-Dimethyl-4-(2-nitro-4-chlorobenzoyl)-5-pyrazolyl 4-toluenesulfonate.5. 1,3-Dimethyl-4-(2-nitro-4-chlorobenzoyl)-5-pyrazolylbenzenesulfonate. 6.1-Ethyl-3-methyl-4-(2,4-dichlorobenzoyl)-5-pyrazolyl 4-toluenesulfonate.7. 1-Ethyl-3-methyl-4-(2-nitro-4-chlorobenzoyl)-5-pyrazolyl4-toluenesulfonate. 8.1-Allyl-3-methyl-4-(2-chloro-4-nitrobenzoyl)-5-pyrazolyl4-toluenesulfonate.